Silver halide color photographic material having improved dye image stability

ABSTRACT

The present inventioin calls for a silver halide color photographic material comprising a support having thereon at least one silver halide photographic emulsion layer containing a dispersion of oleophilic fine particles containing at least one diffusion resistant oil-soluble coupler which forms a substantially nondiffusible dye upon coupling with an oxidation product of an aromatic primary amine developing agent and at least one water-immiscible coupler solvent having a melting point of not more than 100° C. and a boiling point of not less than 140° C., wherein said oil-soluble coupler is represented by formula (Cp-I), (Cp-II) or (Cp-III) the dispersion of oleophilic fine particles is a dispersion obtained by emulsifying or dispersing a mixture containing at least one of the above couplers, at least one of the above coupler solvents and at least one water-insoluble and organic solvent-soluble homopolymer or copolymer composed of at least one repeating unit which does not have an acid group in the main chain or side chain thereof. 
     The silver halide color photographic material can provide dye images, the prevention from light fading and dark fading of which is well balanced, and which exhibit excellent image preservability when exposed to high temperature and high humidity as well as when exposed to light.

FIELD OF THE INVENTION

The present invention relates to a silver halide color photographicmaterial, and more particularly relates to a silver halide colorphotographic material which provides dye images having improvedpreservability.

BACKGROUND OF THE INVENTION

It is known that dye images formed from silver halide color photographicmaterials are sometimes permitted to be exposed to irradiation by lightfor a long period of time or are left in a dark place for a long timewith only a short period of irradiation to light. These conditions cancause severe fading of the dye image. In general, fading under the firstcircumstance is known as light fading and fading under the secondcircumstance is called dark fading. When records formed from colorphotographic light-sensitive material are semipermanently stored,control over such light fading and dark fading to as great an extent aspossible and maintenance of three color balance in the fading of yellow,magenta and cyan dye images are necessary so that the initial state ofcolor balance is maintained. However, the degree of light fading anddark fading of yellow, magenta and cyan dye images are different fromeach other and, thus, the three color balance of yellow, magenta andcyan dye images is destroyed, resulting in degradation of image quality.

Although the degree of light fading and dark fading is naturallydifferent depending on the particular color couplers employed and otherfactors, in many cases dark fading is apt to occur in the order of cyandye images, yellow dye images and magenta dye images, and the degree ofdark fading in cyan dye images is particularly great compared with thatof other dye images. Light fading also tends to occur in the order ofcyan dye images, yellow dye images and magenta dye images, particularlywhen the light source is emitting a large amount of ultraviolet rays.

Therefore, maximum prevention of light fading and dark fading of cyandye images is necessary in order to maintain three color balance betweenyellow, magenta and cyan dye images for a long period of time. For thepurpose of preventing light fading and dark fading of dye images,various kinds of investigations have been heretofore made, which mainlyhave followed to approaches to the problem. One approach has been todevelop novel couplers which can form dye images having less a tendencyto fade. The other approach has been to develop novel additives capableof preventing fading.

A large number of phenol type cyan couplers which form cyan dyes areknown. However,2-(α-2,4-di-tert-amylphenoxybutanamido)-4,6-dichloro-5-methylphenol asdescribed in U.S. Pat. No. 2,801,171, for example, has the disadvantagethat the dye formed therefrom has poor heat fastness while it has goodlight fastness.

Further, cyan couplers having an alkyl group containing 2 or more carbonatoms substituted on the 3-position or 5-position of phenol aredescribed, for example, in Japanese Patent Publication No. 11572/74,Japanese Patent Application (OPI) Nos. 209735/85 and 205447/85 (the term"OPI" as used herein refers to a "published unexamined Japanese patentapplication"), etc. The heat fastness of cyan images formed from thesecouplers is improved to some extent but still insufficient.

Moreover, 2,5-diacylaminophenol type cyan couplers in which the2-position and 5-position of the phenol are substituted with anacylamino group are described, for example, in U.S. Patents 2,369,929,2,772,162 and 2,895,826, Japanese Patent Application (OPI) Nos.112038/75, 109630/78 and 163537/80, etc. Although the heat fastness ofcyan images formed from these 2,5-diacylaminophenol type cyan couplersis improved, their color forming property is poor, cyan images formedtherefrom are sensitive to light fading and yellow stain is apt to occurdue to irradiation or the unreacted cyan couplers to light. Also,further improvement in heat fastness is required.

1-Hydroxy-2-naphthamide type cyan couplers are generally notsatisfactory with regard to both light fading and dark fading.

Further, 1-hydroxy-2-acylaminocarbostyryl type cyan couplers asdescribed in Japanese Patent Application (OPI) No. 104333/81 areexcellent in fastness to light and heat, but the spectral absorptioncharacteristics of the color images formed therefrom are not preferredfor color reproduction.. In addition, they have the problem that pinkstain occurs upon irradiation to light.

Moreover, cyan polymer couplers as described in U.S. Pat. No. 3,767,412,Japanese Patent Application (OPI) Nos. 65844/84 and 39044/86, etc., areexcellent in heat fastness under dry conditions, but are poor in heatfastness and color forming property under high humidity.

Furthermore, a method wherein a hydrophobic substance such as anoil-soluble coupler is dissolved in a water-miscible organic solvent andthe solution is mixed with a loadable polymer latex whereby thehydrophobic substance is loaded in the polymer latex is described inU.S. Pat. No. 4,203,716, etc. However, the method using such a loadablepolymer latex has the disadvantage that cyan images are particularlyinferior in light fastness in comparison with a water-immiscible couplersolvent having a high boiling point. In addition, it is necessary toemploy the polymer in a large amount in order to load a sufficientamount of coupler to obtain a sufficiently high maximum color density.Still further, Japanese Patent Publication No. 30494/73 describes aphotographic material containing a coupler dispersion (diameter ofdispersion particles being about 0.5 μm to 5 μm) which is prepared byusing an organic solvent-soluble homopolymer of a hydrophobic monomerhaving a specific structure or copolymer of a hydrophobic monomer havinga specific structure and a hydrophobic monomer having a specificstructure in place of the coupler solvent having a high boiling point.Improved physical properties of the layer, improved recoloring ability,light fastness and preservability before photographic processing, etc.,are achieved. However, in the case wherein the homopolymer of ahydrophobic monomer as described in Japanese Patent Publication No.30494/73 is employed in place of the coupler solvent, low color formingability is encountered. This tendency particularly manifests itself(when a color developing solution which does not substantially contain acolor forming accelerator such as benzyl alcohol is used), as disclosedin the examples of the above-described patent publication. Anotherproblem is that the stability of the emulsified dispersion is poor.

On the other hand, when using a copolymer containing a hydrophilicmonomer such as acrylic acid, etc., the stability of the emulsifieddispersion and color forming ability are improved to some extent, butare still insufficient. Further, when the ratio of hydrophilic monomerin the copolymer is increased in order to improve color forming ability,fading, (particularly heat fading at high humidity), is accelerated. Inaddition, both polymers have the problem of crystallization of couplersduring storage of the emulsified dispersion, etc., because the polymersare inferior in preventing the crystallization of couplers.

Further, when the method as described in Japanese Patent Publication No.30494/73 is applied to cyan couplers, light fastness is severelydegraded (1.5 to 3 times) compared with when the couplers are dispersedusing a conventional solvent having a high boiling point (known as theoil dispersing method).

In addition, with the method as described in Japanese Patent PublicationNo. 30494/73, further problem is that the hue of cyan dyes changes overtime. More specifically, the spectral absorption of cyan dyes formedupon color development is in a longer wavelength range just afterdevelopment processing but readily shifts to a shorter wavelength duringstorage, particularly when exposed to high temperatures.

As described above, couplers that prevent dark fading because ofmodification of their structure have significant disadvantages withregard to hue, color forming ability, stain, and/or light fastness.Therefore, a novel way to avoid these problems has been desired.

Also, a way to prevent dark fading using other additives or dispersingmethods which are known has certain problems and an effective means freefrom such disadvantages has not been found heretofore.

With regard to color development of silver halide color photographicmaterials containing oleophilic diffusion resistant type (oil protectedtype) couplers, various permeating agents for color developing agentshave been investigated in order to increase their color forming abilityand to shorten processing time. In particular, adding benzyl alcohol toa color developing solution has a large accelerating effect on colorformation and, therefore, is widely utilized at present in theprocessing of color paper, color reversal paper or color positive filmsfor display, etc.

When this approach is used, a further solvent such as diethylene glycol,triethylene glycol, an alkanolamine, etc., is required in order toassist dissolution, since benzyl alcohol has low water solubility. Thiscombination of benzyl alcohol with additional solvents places a highload on the environment due to environmental pollution such as BOD(biochemical oxygen demand) and COD (chemical oxygen demand). Therefore,it is desirable to eliminate these compounds from the processingsolution for the purpose of protection of the environment.

Also, it takes a long time to dissolve benzyl alcohol in a developingsolution even when such a solvent is employed and, thus, it ispreferable not to utilize benzyl alcohol in order to simplifypreparation of the solution.

Further, when benzyl alcohol is carried over into the bath following thecolor developing solution such as a bleaching bath or a bleach-fixingbath, it can cause the formation of leuco dyes of cyan dyes resulting indecreased color density. Moreover, benzyl alcohol retards the rate forrunning components contained in the developing solution out ofphotographic materials and sometimes deteriorates the preservability ofimages in the photographic materials after processing. For thesereasons, it is desirable that benzyl alcohol not be used.

Accordingly, a coupler dispersion having improved image preservabilityas well as excellent color forming property without using benzyl alcoholhas been desired.

Therefore, a first object of the present invention is to provide asilver halide color photographic material which can form dye images inwhich light fading and dark fading are controlled in good balance andwhich exhibits excellent image preservability particularly when exposedto high temperature and high humidity.

A second object of the present invention is to provide a silver halidecolor photographic material which can form dye images having good colorbalance in the fading of yellow, magenta and cyan color images bycontrolling the degree of fading, whereby excellent preservability isobtained when the photographic material is stored for a long period oftime.

Third object of the present invention is to provide a silver halidecolor photographic material which can form dye images having improvedimage preservability without adversely affecting the desired propertiesof the photographic material.

A fourth object of the present invention is to provide a silver halidecolor photographic material having excellent image preservability whichcontains a coupler emulsified dispersion which exhibits sufficientlyhigh color forming property even when processed with a color developingsolution which does not substantially contain benzyl alcohol and hasgood stability.

A fifth object of the present invention is to provide a silver halidecolor photographic material having improved dark fastness withoutdegradation of light fastness of cyan dye images.

DESCRIPTION OF THE INVENTION

As a result of various investigations, it has been found that theseobjects of the present invention can be accomplished with a silverhalide color photographic material comprising a support having thereonat least one silver halide photographic emulsion layer containing adispersion of oleophilic fine particles containing at least onediffusion resistant oil-soluble coupler which forms a substantiallynondiffusible dye upon coupling with an oxidation product of an aromaticprimary amine developing agent and at least one water-immiscible couplersolvent having a melting point of not more than 100° C. and a boilingpoint of not less than 140° C., wherein said oil-soluble coupler isrepresented by formula (Cp-I), (Cp-II) or (Cp-III) as defined below andthe dispersion of oleophilic fine particles is a dispersion obtained byemulsifying or dispersing a mixture solution containing at least one ofthe couplers, at least one of the coupler solvents and at least onewater-insoluble and organic solvent-soluble homopolymer or copolymercomposed of at least one repeating unit in an amount of not less than 35mol% which does not have an acid group in the main chain or side chainthereof; ##STR1## wherein R³¹ represents an alkyl group, a cycloalkylgroup, an aryl group or a heterocyclic group; R³² represents anacylamino group, or an alkyl group having 2 or more carbon atoms; R³³represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxygroup; with proviso R³¹ represents an aryl group when R³² is anacylamino group; Z³¹ represents a hydrogen atom, or a releasable groupwhen Z³¹ reacts with an oxidation products of an aromatic primary aminecolor developing agent. ##STR2## wherein Ar represents an aryl group;R²¹ represents a hydrogen atom, an acyl group, or an aliphatic oraromatic sulfonyl group; R²² represents a halogen atom, or an alkoxygroup; R²³ represents an alkyl group, an aryl group, a halogen atom, analkoxy group, an aryloxy group, an acylamino group, an imido group, asulfonamido group, an alkoxycarbonyl group, a carbamoyl group, asulfamoyl group, an alkylthio group, or a sulfonyl group; R²⁷ representsan alkyl group, an alkoxy group, or an aryloxy group; R²⁹ represents ahydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, analkoxy group, or an aryl group; R²⁸ represents an amino group, acylaminogroup, an ureido group, an alkoxy carbonylamino group, an imido group, asulfonamido group, a sulfamoylamino group, an alkoxycarbonyl group, acarbamoyl group, an acyl group, a cyano group, or an alkylthio group;provided that at least one of R²⁷ and R²⁹ represents an alkoxy group; m¹and m² each represents an integer of 1 to 4; and m³ represent 0 or aninteger of 1 to 3. ##STR3## wherein R²⁴ represents a hydrogen atom or asubstituent group; Z²¹ represents a hydrogen atom or a releasable groupwhen Z²¹ reacts with an oxidatized product of an aromatic primary aminecolor developing agent; Z²², Z²³ and Z²⁴ each represents ##STR4## --N═or --NH--, including that at least one of bondings Z²⁴ --Z²³ and Z²³--Z²² is double-bond and the rest thereof is a single-bond, and abonding Z²³ --Z²² is a part of an aromatic ring when Z²³ --Z²² is acarbon to carbon double-bond.

The term "acid group" as used herein with respect to the polymer meansthe remainder which is formed by eliminating a hydrogen atom capable ofbeing substituted with a metal from an acid molecule and constitutes anegative portion of a salt.

The repeating unit which does not have an acid group includes arepeating unit which does not contain a carboxylic acid group, asulfonic acid group, a phenol or naphthol moiety having at least oneelectron withdrawing group at the ortho position and the para positionto the hydroxy group thereof and a pKa of not more than about 10, and anactive methylene moiety, or a salt thereof. Therefore, a coupler moietyis deemed as the acid group in the present invention.

BEST MODE TO CARRY OUT THE INVENTION

In the present invention, followings are illustrated as preferredembodiments.

(1) A silver halide color photographic material wherein the repeatingunit which does not contain an acid group has a group of ##STR5## in amain or side chain.

(2) A silver halide color photographic material wherein the repeatingunit which does not contain an acid group has a group of ##STR6## in amain or side chain.

(3) A silver halide color photographic material wherein the repeatingunit which does not contain an acid group has a group of ##STR7##(wherein G₂ and G₂ each represents a hydrogen atom, substituted orunsubstituted alkyl group, or substituted or unsubstituted aryl group).

(4) A silver halide color photographic material, wherein said repeatingunits of polymer free of acid radical is a repeating unit having thefollowing definition (A):

Definition (A): The glass transition point (Tg) of a monopolymer with amolecular weight of 20,000 or more containing only said repeating unitsis 50° C. or above.

(5) A silver halide color photographic material, containing at least onecoupler of the general formula (Cp-I) as a cyan coupler and at least onecoupler of the general formula (Cp-II) and/or the general formula(Cp-III) as a magenta coupler among said oil-soluble couplers.

(6) A silver halide color photographic material wherein the couplersolvent is represented by the following formula (III), (IV), (V), (VI),(VII) or (VIII): ##STR8## wherein W₁, W₂ and W₃ each represents asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted alkenyl group, asubstituted or unsubstituted aryl group or a substituted orunsubstituted heterocyclic group; W4 represents W₁, --O--W₁ or --S--W₁ ;n represents an integer from 1 to 5 and when n is two or more, two ormore W₄ 's may be the same or different; W₁ and W₂ in the formula (VII)maY combine to form a condensed ring; W₆ represents a substituted orunsubstituted alkyl group or a substituted or unsubstituted aryl groupand the total number of carbon atoms in W₆ is not less than 12.

(7) A silver halide color photographic material wherein the silverhalide photographic material is treated with a developing agent whichdoes not substantially contain a benzyl alcohol after exposure to alight, in which a color developing agent herein means a color developingsolution contains a benzyl alcohol in a concentration of 0.5 ml/l orlesser in the developing solution, and preferably, no benzyl alcoholcontains.

The polymer which can be employed in the present invention may be anypolymer composed of at least one repeating unit which does not containthe acid group in the main chain or side chain thereof and beingwater-insoluble and organic solvent-soluble. Of those polymers, thosecomposed of a repeating unit having a linkage of ##STR9## are preferredin view of color forming property and effect on preventing fading.

On the contrary, when a polymer composed of a monomer containing theacid group is employed, the effect on the prevention from fading due tothe polymer is greatly reduced and such a polymer is not desirable. Thereason for this is not clear.

Monomers providing a repeating unit having no acid group are preferablyselected from compounds whose homopolymers (having a molecular weight ofat least 20,000) have a glass transition point (Tg) of 50° C. or higher,and more preferably 80° C. or higher. Polymers comprising monomers whosehomopolymers have a Tg of less than 50° C. surely produce an effect onimprovement of image fastness in accelerated deterioration test at ahigh temperature (above 80° C.). However, as the temperature approachesto room temperature, the effect is reduced and becomes insubstantial asif no polymer is added. To the contrary, when polymers. comprisingmonomers whose homopolymers have a Tg of about 50° C. or higher areused, the effect as attained under a high temperature condition can beheld or even heightened as the temperature approaches to roomtemperature. In particular, the improving effect is markedly enhancedwhen polymers comprising monomers whose homopolymers have a high Tg (80°C. or higher). This favorable trend is acrylamide monomers ormethacrylamide monomers.

Further, polymers producing greater effects on improvement ofheat-fastness tend to have so much effects on improvement oflight-fastness. The improving effects are particularly pronounced in lowdensity areas.

The proportion of the repeating unit having no acid radical in thepolymers of the present invention is at least 35 mol%, preferably atleast 50 mol%, and more preferably from 70 to 100 mol%.

The polymers which can be used in the present invention are explained inmore detail with reference to specific examples thereof, but the presentinvention should not be construed as being limited to these polymers.

(A) Vinyl polymers:

Monomers for forming a vinyl polymer used in the present inventioninclude an acrylic acid ester, a methacrylic acid ester, a vinyl ester,an acrylamide, a methacrylamide, an olefin, a styrene, a vinyl ether andother vinyl monomers.

Specific examples of acrylic acid esters include methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amylacrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate,tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate,4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate,dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate,2chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfurylacrylate, phenyl acrylate, 5-hydroxypentyl acrylate,2,2-dimethyl-3-hydroxypropyl acrylate, 2methoxyethyl acrylate,3-methoxybutyl acrylate, 2ethoxyethyl acrylate, 2-isopropoxy acrylate,2butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate,2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate(addition molar number n =9), 1-bromo-2-methoxyethyl acrylate,1,1-dichloro-2-ethoxyethyl acrylate, etc.

Methacrylic acid esters: Specific examples thereof methacrylate,n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate,amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzylmethacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearylmethacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethylmethacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate,dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate,tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresylmethacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate,4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate,dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate,3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate,2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,2-isopropoxyethyl methacrylate, 2-butoxyethyl methacrylate,2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethylmethacrylate, 2(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethyleneglycol methacrylate (addition molar number u =6), allyl methacrylate,dimethylaminoethyl methacrylate methyl chloride salt, etc.

Vinyl esters: Specific examples thereof include vinyl acetate, vinylpropionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinylchloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinylbenzoate, vinyl salicylate, etc.

Acrylamides: Specific examples thereof include acrylamide,methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide,tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide,hydroxymethylacrylamide, methoxyethylacrylamide,dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide,diethylacrylamide, β-cyanoethylacrylamide,N-(2-acetoacetoxyethyl)acrylamide, diacetonacrylamide, etc.

Methacrylamide: Specific examples thereof include methacrylamide,methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide,butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide,benzylmethacrylamide, hydroxymethylmethacrylamide,methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide,phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide,β-cyanoethylmethacrylamide, N-(2-acetoacetoxyethyl)-methacrylamide, etc.

Olefins: Specific examples thereof include dicyclopentadiene, ethylene,propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride,isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc.

Specific examples of styrenes include styrene, methylstyrene,dimethylstyrene, trimethylstyrene, isopropylstyrene,chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene,dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, etc.

Vinyl ethers: Specific examples thereof include methyl vinyl ether,butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether,dimethylaminoethyl vinyl ether, etc.

Specific examples of other vinyl monomers include butyl crotonate, hexylcrotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate,dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate,dibutyl fumarate, methyl vinyl ketone, methoxyethyl vinyl ketone,glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinylidene chloride,methylene malononitrile, vinylidene, etc.

Two or more kinds of monomers (for example, those as described above)can be employed as comonomer to prepare the polymers according to thepresent invention depending on the particular objective to be satisfied(for example, improvement in the solubility thereof, etc.). Further, forthe purpose of adjusting color forming ability and solubility of thepolymers, a monomer having an acid group as illustrated below can beemployed as a comonomer within the scope of the present invention solong as the copolymer obtained is not rendered watersoluble.

Specific examples of such monomers having an acid group include acrylicacid; methacrylic acid; itaconic acid; maleic acid; a monoalkylitaconate, for example monomethyl itaconate, monethyl itaconate,monobutyl itaconate, etc.; a monoalkyl maleate, for example, monomethylmaleate, monoethyl maleate, monobutyl maleate, etc.; citraconic acid;styrene sulfonic acid; vinylbenzylsulfonic acid; vinylsulfonic acid; anacryloyloxyalkylsulfonic acid, for example acryloyloxymethylsulfonicacid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid,etc.; a methacryloyloxyalkylsulfonic acid, for examplemethacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid,methacryloyloxypropylsulfonic acid, etc.; an acrylaminoalkylsulfonicacid, for example, 2-acrylamido-2-methylethanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-acrylamido-2-methylbutanesulfonic acid, etc.; amethacrylamidoalkylsulfonic acid, for example,2-methacrylamido-2-methylethanesulfonic acid,2-methacrylamido-2-methylpropanesulfonic acid,2-methacrylamido-2-methylbutanesulfonic acid, etc.; etc.

The acid may be in the form of a salt of an alkali metal, for example,sodium, potassium, etc., or an ammonium ion.

In the case where the vinyl monomer described above and a hydrophilicvinyl monomer (which forms a hydrophilic homopolymer used in the presentinvention is employed) as a comonomer, a ratio of the hydrophilicmonomer contained in the copolymer is not strictly limited so long asthe copolymer is not rendered watersoluble. The percent hydrophilicmonomer contained in the copolymer is preferably not more than 40% permol copolymer, more preferably not more than 20% per mol copolymer, andfurther more preferably not more than 10% per mol copolymer. Further,when a hydrophilic comonomer copolymerizable with the monomer of thepresent invention has an acid group, the percent comonomer having anacid group contained in the copolymer is usually not more than 20% permol comonomer, and preferably not more than 10% per mol comonomer. Inthe most preferred case the copolymer does not contain such a monomer.

Preferred monomers for preparing the polymer according to the presentinvention are methacrylate type monomers, acrylamide type monomers andmethacrylamide type monomers. Most preferred monomers are acrylamidetype monomers and methacrylamide monomers.

(B) Polyester resins obtained by condensation of polyvalent alcohols andpolybasic acids:

Useful polyvalent alcohols include a glycol having a structure of HO--R₁--OH (wherein R₁ represents a hydrocarbon chain having from 2 to about12 carbon atoms, particularly an aliphatic hydrocarbon chain) and apolyalkylene glycol, and useful polybasic acids include thoserepresented by the formula HOOC--R₂ --COOH (wherein R₂ represents asingle bond or a hydrocarbon chain having from 1 to about 12 carbonatoms).

Specific examples of the polyvalent alcohols include ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, trimethylol propane, 1,4-butanediol,isobutylenediol, 1,5-pentanediol, neopentyl glycol, 1,6hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, glycerol,diglycerol, triglycerol, 1-methylglycerol, erythritol, mannitol,sorbitol, etc.

Specific examples of polybasic acids include oxalic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, iso-pimelic acid, azelaicacid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid,undecanedicarboxylic acid, dodecanecarboxylic acid, fumaric acid, maleicacid, itaconic acid, citraconic acid, phthalic acid, isophthalate,terephthalate, tetrachlorophthalate, mesaconic acid, isopimelic acid,cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct,etc.

(C) Other polymers:

A polyester obtained by open ring condensation as shown below isexemplified. ##STR10## wherein m represents an integer from 4 to 7 andthe --CH₂ -- chain may be a branched chain.

Two or more of the polymers of the present invention disclosed above mayoptionally be used in combination.

Suitable monomers for preparation of the polyester includeβ-propiolactone, ε-caprolactone, dimethylpropiolactone, etc.

Molecular weight and degree of polymerization of the polymer accordingto the present invention do not have a substantial influence on theproperties exhibited by the present invention. However, as the molecularweight becomes higher, some problems are apt to occur, such as a slowrate of dissolution in an auxiliary solvent and difficult emulsificationor dispersion thereof due to the high viscosity of the solution. Thedifficult emulsification or dispersion causes coarse grains to beformed, which, in turn, results in a decrease in color forming abilityand coating ability.

When a large amount of the auxiliary solvent is used to reduce itsviscosity in order to traverse such difficulties, new problems in theprocess may occur.

The viscosity of the polymer is preferably not more than 5,000 cps, morepreferably not more than 2,000 cps when 30 g of the polymer is dissolvedin 100 ml of auxiliary solvent. Also, the molecular weight of thepolymer to be used in the present invention is preferably not more than150,000, more preferably not more than 80,000 and further morepreferably not more than 30,000.

The ratio of polymer to auxiliary solvent depends upon the kind ofpolymer used and can be varied over a wide range depending on itssolubility in the auxiliary solvent, its degree of polymerization, andthe solubility of the coupler, etc. Usually the auxiliary solvent isemployed in an amount necessary to make the viscosity sufficiently lowfor easily dispersing a solution containing at least a coupler, acoupler solvent having a high boiling point and the polymer dissolved inthe auxiliary solvent in water or an aqueous solution of a hydrophiliccolloid. Since the viscosity of the solution increases with the degreeof polymerization of the polymer, it is difficult to set forth a ratioof the polymer to an auxiliary solvent that wold apply to every polymer.The ratio depends on the kind of the polymer employed. Usually, however,a ratio of about 1:1 to about 1:50 (by weight) is preferred. A ratio ofthe polymer according to the present invention to a coupler ispreferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 (byweight).

The polymers which can be used in the present invention are illustratedin part as set forth below, but the present invention should not beconstrued as being limited to these polymers.

    ______________________________________                                        Examples                                                                             Polymers                Tg (°C.)                                ______________________________________                                        P-1    Polyvinylacetate        32                                             P-2    Polyvinylpropionate     20                                             P-3    Polymethylmethacrylate  105                                            P-4    Polyethylmethacrylate   65                                             P-5    Polyethylacrylate       -24                                            P-6    Copolymer of vinylacetate-vinyl-                                                                      (32)                                                  alcohol (95:5)                                                         P-7    Poly(n-butylacrylate)   -54                                            P-8    Poly(n-butylmethcrylate)                                                                              20                                             P-9    Poly(iso-butylmethacrylate)                                                                           53                                             P-10   Poly(iso-propylmethacrylate)                                                                          81                                             P-11   Poly(decylmethacrylate) -70                                            P-12   Copolymer of n-butylacrylate-acryl-                                                                   (-54)                                                 amide (95:5)                                                           P-13   Polymethylacrylate      140                                            P-14   Poly(butanediol.adipate)                                                                              -68                                            P-15   Poly(ethyleneglycol sebacate)                                                                         --                                             P-16   Polycaprolactone        --                                             P-17   Poly(2-tert-butylphenyl acrylate)                                                                     72                                             P-18   Poly(4-tert-butylphenyl acrylate)                                                                     71                                             P-19   Copolymer of n-butylmethacrylate-N-                                                                   (20)                                                  vinyl-2-pyrrolidone (90:10)                                            P-20   Copolymer of methylmethacrylate-                                                                      (105)                                                 vinyl chloride (70:30)                                                 P-21   Copolymer of methylmethacrylate-                                                                      (105)                                                 styrene (90:10)                                                        P-22   Copolymer of methylmethacrylate-                                                                      (105, -24)                                            ethylacrylate (50:50)                                                  P-23   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  methylmethacrylate.styrene (50:30:20)                                  P-24   Copolymer of vinylacetate-acrylamide                                                                  (32)                                                  (85:15)                                                                P-25   Copolymer of vinyl chloride-vinyl-                                                                    (81)                                                  acetate (65:35)                                                        P-26   Copolymer of methylmethacrylate-                                                                      (105)                                                 acrylonitrile (65:35)                                                  P-27   Copolymer of diacetoneacrylamide-                                                                     (60, 105)                                             methylmethacrylate (50:50)                                             P-28   Copolymer of vinylmethylketone-iso-                                                                   (--, 53)                                              butylmethacrylate (55:45)                                              P-29   Copolymer of ethylmethacrylate-n-                                                                     (65)                                                  butylacrylate (70:30)                                                  P-30   Copolymer of diacetoneacrylamide-                                                                     (60, -54)                                             n-butylacrylate (60:40)                                                P-31   Copolymer of methylmethacrylate                                                                       (105, 104)                                            cyclohexylmethacrylate (50:50)                                         P-32   Copolymer of n-butylacrylate-                                                                         (-54)                                                 styrenemethacrylate-diacetone-                                                acrylamide (70:20:10:)                                                 P-33   Copolymer of N-tert-butylmethacryl-                                                                   (160, 105)                                            amide-methylmethacrylate-acrylate                                             (60:30:10)                                                             P-34   Copolymer of methylmethacrylate-                                                                      (105)                                                 styrene-vinylsulfoneamide                                                     (70:20:10)                                                             P-35   Copolymer of methylmethacrylate-                                                                      (105)                                                 phenylvinylketone (70:30)                                              P-36   Copolymer of butylacrylate-methyl-                                                                    (-54, 105)                                            methacrylate-n-butylmethacrylate                                              (35:35:30)                                                             P-37   Copolymer of n-butylmethacrylate-                                                                     (20, -5)                                              pentylmethacrylate-N-vinyl-2-                                                 pyrrolidone                                                            P-38   Copolymer of methylmethacrylate-n-                                                                    (105)                                                 butylmethacrylate-isobutylmeth-                                               acrylate-acrylate (37:29:25:9)                                         P-39   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  acrylate (95:5)                                                        P-40   Copolymer of methylmethacrylate-                                                                      (105)                                                 acrylate (95:5)                                                        P-41   Copolymer of benzylmethacrylate-                                                                      (54)                                                  acrylate (90:10)                                                       P-42   Copolymer of n-butylmethacrylate-                                                                     (20, 105)                                             methylmethacrylate-benzylmeth-                                                acrylate (35:35:25:5)                                                  P-43   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  methylmethacrylate-benzylmethacry-                                            late (35:35:30)                                                        P-44   Poly(3-pentylacrylate)  (-6)                                           P-45   Copolymer of cyclohexylmethacrylate-                                                                  (104)                                                 methylmethacrylate-n-propylmeth-                                              acrylate (37:29:34)                                                    P-46   Poly(pentylmethacrylate)                                                                              -5                                             P-47   Copolymer of methylmethacrylate-n-                                                                    (105, 20)                                             butylmethacrylate (65:35)                                              P-48   Copolymer of vinylacetate-vinyl-                                                                      (32)                                                  propionate (75:25)                                                     P-49   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  sodium-3-acryloxybutane-1-sulfonate                                           (97:3)                                                                 P-50   Copolymer of n-butylmethacrylate-                                                                     (20, 105)                                             methylmethacrylate-acrylamide                                                 (35:35:30)                                                             P-51   Copolymer of n-butylmethacrylate-                                                                     (20, 105)                                             methylmethacrylate-vinyl chloride                                             (37:36:27)                                                             P-52   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  styrene (90:10)                                                        P-53   Copolymer of methylmethacrylate-N-                                                                    (105)                                                 vinyl-2-pyrrolidone                                                    P-54   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  vinylchloride (90:10)                                                  P-55   Copolymer of n-butylmethacrylate-                                                                     (20)                                                  styrene (70:30)                                                        P-56   Poly(N-sec-butylacrylamide)                                                                           117                                            P-57   Poly(N-tert-butylacrylamide)                                                                          128                                            P-58   Copolymer of diacetoneacrylamide-                                                                     (60, 105)                                             methylmethacrylate (62:38)                                             P-59   Copolymer of poly(cyclohexylmeth-                                                                     (104, 105)                                            acrylate)-methylmethacrylate                                                  (60:40)                                                                P-60   Copolymer of N-tert-butylacryl-                                                                       (128, 105)                                            amide-methylmethacrylate (40:60)                                       P-61   Poly(N-n-butylacrylamide)                                                                             46                                             P-62   Copolymer of poly(tert-butylacry-                                                                     (118, 128)                                            late)-N-tert-butylacrylamide                                                  (50:50)                                                                P-63   Copolymer of tert-butylmethacrylate-                                                                  (118)                                                 methylmethacrylate (70:30)                                             P-64   Poly(N-tert-butylmethacrylamide)                                                                      160                                            P-65   Copolymer of N-tert-butylacryl-                                                                       (128, 105)                                            amide-methylmethacrylate (60:40)                                       P-66   Copolymer of methylmethacrylate-                                                                      (105)                                                 acrylonitrile (70:30)                                                  P-67   Copolymer of methylmethacrylate-                                                                      (105, --)                                             vinylmethylketone nylmethylketone (38:62)                              P-68   Copolymer of methylmethacrylate-                                                                      (105)                                                 styrene (75:25)                                                        P-69   Copolymer of methylmethacrylate-                                                                      (105)                                                 hexylmethacrylate (70:30)                                              P-70   Poly(benzylacrylate)    6                                              P-71   Poly(4-biphenylacrylate)                                                                              110                                            P-72   Poly(4-butoxycarbonyl phenylacrylate)                                                                 13                                             P-73   Poly(sec-butylacrylate) -22                                            P-74   Poly(tert-butylacrylate)                                                                              43                                             P-75   Poly[3-chloro-2,2-bis(chloromethyl)-                                                                  46                                                    propylacrylate]                                                        P-76   Poly(2-chlorophenylacrylate)                                                                          53                                             P-77   Poly(4-chlorophenyl acrylate)                                                                         58                                             P-78   Poly(pentachlorophenyl acrylate)                                                                      147                                            P-79   Poly(4-cyanobenzyl acrylate)                                                                          44                                             P-80   Poly(cyanoethyl acrylate)                                                                             4                                              P-81   Poly(4-cyanophenyl acrylate)                                                                          90                                             P-82   Poly(4-cyano-3-thiabutyl acrylate)                                                                    -24                                            P-83   Poly(cyclohexyl acrylate)                                                                             19                                             P-84   Poly(2-ethoxycarbonylphenyl acrylate)                                                                 30                                             P-85   Poly(3-ethoxycarbonylphenyl acrylate)                                                                 24                                             P-86   Poly(4-ethoxycarbonylphenyl acrylate)                                                                 37                                             P-87   Poly(2-ethoxyethyl acrylate)                                                                          -50                                            P-88   Poly(3-ethoxypropyl acrylate)                                                                         -55                                            P-89   Poly(1H,1H,5H-octafluoropentyl                                                                        -35                                                   acrylate)                                                              P-90   Poly(heptyl acrylate)   -60                                            P-91   Poly(hexadecyl acrylate)                                                                              35                                             P-92   Poly(hexyl acrylate)    -57                                            P-93   Poly(iso-butyl acrylate)                                                                              -24                                            P-94   Poly(iso-propyl acrylate)                                                                             -5                                             P-95   Poly(3-methoxybutyl acrylate)                                                                         -56                                            P-96   Poly(2-methoxycarbonylphenyl acrylate)                                                                46                                             P-97   Poly(3-methoxycarbonylphenyl acrylate)                                                                38                                             P-98   Poly(4-methoxycarbonylphenyl acrylate)                                                                67                                             P-99   Poly(2-methoxyethyl acrylate)                                                                         -50                                            P-100  Poly(4-methoxyphenyl acrylate)                                                                        51                                             P-101  Poly(3-methoxypropyl acrylate)                                                                        -75                                            P-102  Poly(3,5-dimethyladamanthyl acrylate)                                                                 106                                            P-103  Poly(3-dimethylaminophenyl acrylate)                                                                  47                                             P-104  Poly(tert-butylate)     86                                             P-105  Poly(2-methylbutyl acrylate)                                                                          -32                                            P-106  Poly(3-methylbutyl acrylate)                                                                          -45                                            P-107  Poly(1,3-dimethylbutyl acrylate)                                                                      -15                                            P-108  Poly(2-methylpentyl acrylate)                                                                         -38                                            P-109  Poly(2-naphtyl acrylate)                                                                              85                                             P-110  Poly(phenyl acrylate)   57                                             P-111  Poly(propyl acrylate    -37                                            P-112  Poly(m-tolyl acrylate)  25                                             P-113  Poly(o-tolyl acrylate)  52                                             P-114  Poly(p-tolyl acrylate)  43                                             P-115  Poly(N,N-dibutyl acrylamide)                                                                          60                                             P-116  Poly(iso-henxyl acrylamide)                                                                           71                                             P-117  Poly(iso-octylacrylamide)                                                                             66                                             P-118  Poly(N-methyl-N-phenylacrylamide)                                                                     180                                            P-119  Poly(adamanthyl methacrylate)                                                                         141                                            P-120  Poly(benzyl methacrylate)                                                                             54                                             P-121  Poly(2-bromoethyl methacrylate)                                                                       52                                             P-122  Poly(2-N-tert-butylaminoethyl                                                                         33                                                    methacrylate)                                                          P-123  Poly(sec-butyl methacrylate)                                                                          60                                             P-124  Poly(tert-butyl methacrylate)                                                                         118                                            P-125  Poly(2-chloroethyl methacrylate)                                                                      92                                             P-126  Poly(2-cyanoethyl methacrylate)                                                                       91                                             P-127  Poly(2-cyanomethylphenyl methacrylate)                                                                128                                            P-128  Poly(4-cyanophenyl methacrylate)                                                                      155                                            P-129  Poly(cyclohexyl methacrylate)                                                                         104                                            P-130  Poly(dodecyl methacrylate)                                                                            -65                                            P-131  Poly(diethylaminoethyl methacrylate)                                                                  -20                                            P-132  Poly(2-ethylsulfinylethyl meth-                                                                       25                                                    acrylate)                                                              P-133  Poly(hexadecyl methacrylate)                                                                          15                                             P-134  Poly(hexyl methacrylate)                                                                              -5                                             P-135  Poly(2-hydroxypropyl methacrylate)                                                                    76                                             P-136  Poly(4-methoxycarbonylphenyl meth-                                                                    106                                                   acrylate)                                                              P-137  Poly(3,5-dimethyladamanthyl meth-                                                                     196                                                   acrylate)                                                              P-138  Poly(dimethylaminoethyl methacrylate)                                                                 20                                             P-139  Poly(3,3-dimethylbutyl methacrylate)                                                                  45                                             P-140  Poly(3,3-dimethyl-2-butyl meth-                                                                       108                                                   acrylate)                                                              P-141  Poly(3,5,5-trimethylhexyl meth-                                                                       1                                                     acrylate)                                                              P-142  Poly(octadecyl methacrylate)                                                                          -100                                           P-143  Poly(tetradecyl methacrylate)                                                                         80                                             P-144  Poly(4-butoxycarbonylphenyl meth-                                                                     128                                                   acrylamide                                                             P-145  Poly(4-carboxyphenyl methacrylamide)                                                                  200                                            P-146  Poly(4-ethoxycarbonylphenyl meth-                                                                     168                                                   acrylamide)                                                            P-147  Poly(4-methoxycarbonylphenyl meth-                                                                    180                                                   acrylamide)                                                            P-148  Poly(butyl butoxycarbonylmethacrylate)                                                                25                                             P-149  Poly(butyl chloroacrylate)                                                                            57                                             P-150  Poly(butyl cyanoacrylate)                                                                             85                                             P-151  Poly(cyclohexyl chloroacrylate)                                                                       114                                            P-152  Poly(ethyl chloroacrylate)                                                                            93                                             P-153  Poly(ethyl ethoxycarbonylmeth-                                                                        52                                                    acrylate)                                                              P-154  Poly(ethyl ethacrylate) 27                                             P-155  Poly(ethyl fluoromethacrylate)                                                                        43                                             P-156  Poly(hexyl hexyloxycarbonylmeth-                                                                      -4                                                    acrylate)                                                              P-157  Poly(iso-butyl chloroacrylate)                                                                        90                                             P-158  Poly(iso-propyl chloroacrylate)                                                                       90                                             ______________________________________                                         Remarks:                                                                      The data in parentheses shows a glass transition temperature of a             homopolymer of the monomer which does not have an acid group and is           composed of a captioned polymer in an amount of 35% or more.             

An oil soluble coupler providing diffusion resistance according to thepresent invention are described in detail below.

The oil-soluble coupler treated as providing diffusion resistance, whichis herein referred to, is a coupler which is soluble in theaforementioned coupler solvent and is processed to make the couplerdiffusion resistant in a photosensitive material. There are severalmethods for providing diffusion resistance, however, two methods areillustrated hereunder among major methods.

1. A method 1 comprises introducing one or more so-called diffusionresistive groups, a part of which includes an aliphatic group, anaromatic group, or a heterocyclic group. A number of total carbon atomsin the diffusion resistive group is depend on a constituent of aremaining moiety of the coupler, and is, ordinarily, 6 or more, withmore preferably, 12 or more.

2. A method 2 wherein the molecular weight of the coupler is increasedby polymerizing the coupler (known as a polymer coupler) to make thecoupler diffusion resistant.

When the coupler is that produced by Method 1, the molecular weight ofthe coupler is preferably from 250 to 1,200 and more preferably from 300to 800.

When the coupler is that produced by Method 2, a trimer or more ifpreferred.

Examples of cyan couplers in which the above mentioned repeating unit ofpolymer free of acid radical can be used in the present inventioninclude oil protect type naphthol and phenol couplers. Examples of suchnaphthol couplers are described in U.S. Pat. No. 2,474,293. Typicalexamples of preferred such naphthol couplers include oxygenatom-releasing type two-equivalent naphthol couplers as described inU.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Specificexamples of such phenol couplers are described in U.S. Pat. Nos.2,369,939, 2,801,171, 2,772,162, and 2,895,826. Other examples of phenolcouplers which can be preferably used in the present invention includephenol cyan couplers containing an ethyl group or higher alkyl group inthe meta-position of phenol nucleus as described in U.S. Pat. No.3,772,002, 2,5-diacylamino-substituted phenol couplers as described inU.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and4,327,173, West German Patent Disclosure No. 3,329,729, and JapanesePatent Application No. 42671/83, and phenol couplers containing aphenylureide group in the 2-position and an acylamino group in the5-position as described in U.S. Pat. Nos. 3,446,622, 4,333,999,4,451,559, and 4,427,767.

Cyan couplers which can be used in the present invention are phenol cyancouplers of the general formula (Cp-I).

Substituents in the general formula (Cp-I) will be described in detailhereinafter.

In the general formula (Cp-I), examples of C₁₋₃₂ alkyl group representedby R³¹ include methyl group, butyl group, tridecyl group, cyclohexylgroup, and allyl group. Examples of aryl group represented by R³¹include phenyl group, and naphtyl group. Examples of heterocyclic grouprepresented by R³¹ include 2-pyridyl group, and 2-furyl group.

R³¹ may be further substituted by substituents selected from the groupconsisting of alkyl group, aryl group, alkyloxy or aryloxy group such asmethoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert-amylphenoxy,3-tert-butyl-4-hydroxyphenyloxy, and naphthyloxy, carboxy group,alkylcarbonyl or arylcarbonyl group such as acetyl, tetradecanoyl, andbenzoyl, alkyloxycarbonyl or aryloxycarbonyl group such asmethoxycarbonyl, and phenoxycarbonyl, acyloxy group such as acetyl, andbenzoyloxy, sulfamoyl group such as N-ethylsulfamoyl, andN-octadecylsulfamoyl, carbomoyl group such as N-ethylcarbamoyl, andN-methyl-dodecylcarbamoyl, sulfonamide group such as methanesulfonamide,and benzenesulfonamide, acylamino group such as acetylamino, benzamide,ethoxycarbonylamino, and phenylaminocarbonylamino, imide group such assuccinimide, and hydantoinyl, sulfonyl group such as methanesulfonyl,hydroxy group, cyano group, nitro group, and halogen atom.

In the general formula (Cp-I), Z³¹ represents a hydrogen atom, orcoupling-off group. Examples of such a coupling-off group includehalogen atom such as fluorine atom, chlorine atom, and bromine atom,alkoxy group such as dodecyloxy, methoxycarbamoylmethoxy,carboxypropyloxy, and methylsulfonylethoxy, aryloxy group such as4-chlorophenoxy, and 4-methoxyphenoxy, acyloxy group such as acetoxy,tetradecanoyloxy, and benzoyloxy, sulfonyloxy group such asmethanesulfonyloxy, and toluenesulfonyloxy, amide group such asdichloroacetylamino, methanesulfonylamino, and toluenesulfonylamino,alkoxycarbonyloxy group such as ethoxycarbonyloxy, andbenzyloxycarbonyloxy, aryloxycarbonyloxy group such asphenoxycarbonyloxy, aliphatic or aromatic thio group such as phenylthio,2-tutoxy-5-t-octylphenylthio, and tetraxolylthio, imide group such assuccinimide, and hydantoinyl, N-heterocyclic group such as 1-pyraxolyl,and 1-benztriazolyl, and aromatic azo group such as phenylazo. Thesecoupling-off groups may contain photographically useful groups.

In the general formula (Cp-I), examples of acylamino group representedby R³² include acetylamino, benzamide, 2,4-di-tert-amylphenoxyacetamide,α-(2,4-di-tert-amylphenoxy)butylamide,α-(2,4-di-tert-amylphenoxy)-β-methylbutylamide,β-(2-chloro-4-di-ter-amylphenoxy)octanamide,α-(2-chlorophenoxy)tetradecanamide, andα-(3-pentadecylphenoxy)butylamide. Examples of alkyl group containingtwo or more carbon atoms represented by R³² include ethyl, propyl,t-butyl, pentadecyl, and benzyl.

In the general formula (Cp-I), R³³ represents a hydrogen atom, halogenatom such as fluorine atom, chlorine atom, and bromine atom, alkyl groupsuch as methyl, ethyl, n-butyl, n-octyl, and n-tetradecyl, or alkoxygroup such as methoxy, 2-ethylhexyloxy, n-octyloxy, and n-dodecyloxy.

In the general formula (Cp-I), R³¹ or R³² may form a dimer or polymer.

The preferable combination of these couplers are combinations of thecyan coupler (Cp-I) and the polymers which are composed of a monomer inan amount or 50% such that a homopolymer of said monomer shows a Tg of50° C. or higher, more preferably, combinations of the cyan coupler(Cp-I) and the polymers which are composed of a monomer in an amount 70%or more such that a homopolymer of said monomer shows a Tg of 80° C. orhigher, and the most preferably, combinations of the cyan coupler (Cp-I)wherein R₃₂ is an alkyl group having 2 to 4 carbon atoms and polymerswhich are composed of acrylamide type and/or methacrylamide type in anamount of 70% or more such that a homopolymer of said monomer shows a Tgof 80° C. or higher.

As magenta couplers to be used in the present invention, oil protectedindazolone type couplers, cyanoacetyl type couplers, and preferably5-pyrazolone type couplers and pyrazoloazole type couplers such aspyrazolotriazole type couplers are exemplified. Of 5-pyrazolone typecouplers, those substituted with an arylamino group or an acylaminogroup at the 3-position thereof are preferred because of the hue andcolor density of dyes formed therefrom. Typical examples thereof aredescribed in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573,3,062,653, 3,152,896, 3,936,015, etc. 2-Equivalent 5-pyrazolone typecouplers are preferably employed. As releasing groups for 2-equivalent5-pyrazolone type couplers, nitrogen atom releasing groups as describedin U.S. Pat. No. 4,310,619 and arylthio groups as described in U.S. Pat.No. 4,351,897 are preferred. Further, 5-pyrazolone type couplers havinga ballast group as described in European Patent 73,636 are advantageoussince they provide high color density.

Examples of pyrazoloazole type couplers include pyrazolobenzimidazolesas described in U.S. Patent 3,369,879, and preferablypyrazolo[5,1-c][1,2,4]triazoles as described in U.S. Pat. No 3,725,067,pyrazolotetrazoles as described in Research Disclosure, No. 24220 (June,1984) and pyrazolopyrazoles as described in Research Disclosure, No.24230 (June, 1984). Imidazo[1,2-b]-pyrazoles as described in EuropeanPatent 119,741 are preferred and pyrazolo[1,5-b][1,2,4]triazoles asdescribed in European Patent 119,860 are particularly preferred becauseof less yellow subsidiary absorption and light fastness of dyes formedtherefrom and because they are very effective in achieving theobjectives of the present invention.

Examples of magenta couplers which can be more preferably used in thepresent invention include those represented by the general formula(Cp-II) and/or the general formula (Cp-III).

Substituents for the general formula (Cp-II) will be described in detailhereinafter.

Ar represents an aryl group such as phenyl, 2,4,6-trichlorophenyl,2,5-dicholophenyl, 2,6-dichloro-4-methoxyphenyl,2,4-dimethyl-6-methoxyphenyl, 2,6-dichloro-4-ethoxycarbonylphenyl, and2,6-dichloro-4-cyanophenyl. R₂₁ represents a hydrogen atom, acyl groupsuch as acetyl, benzoyl, propanoyl, butanoyl, and monochloroacetyl, oraliphatic or aromatic sulfonyl group such as methanesulfonyl,butanesulfonyl, benzenesulfonyl, toluenesulfonyl, and3-hydroxypropanesulfonyl. R₂₂ represents a halogen atom such as chlorineatom, bromine atom, and fluorine atom, or alkoxy group such as methoxy,butoxy, benzyloxy, and 2-methoxyethoxy. R₂₃ represents an alkyl groupsuch as methyl, butyl, t-butyl, t-octyl, dodecyl,2,4-di-tert-pentylphenoxymethyl, and hexadecyl, aryl group such asphenyl, and 2,4-dichlorophenyl, halogen atom such as chlorine atom,fluorine atom, and bromine atom, alkoxy group such as methoxy,dodecyloxy, benzyloxy, and hexadecyloxy, aryloxy group such as phenoxy,and 4-dodecylphenoxy, acylamino group such as acetylamino,tetradecaneamide, α-(2,4-di-tert-pentylphenoxy)butylamide,α-(4-hydroxy-3-tert-butylphenoxy)tetradecaneamide, andα-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamide, imide group such asN-succinimide, N-maleinimide, 1-N-benzyl-5,5-dimethyl-hydantoin-3-il,and 3-hexadecenyl-1-succinimide, sulfonamide group such asmethanesulfonamide, benzenesulfonamide., tetradecanesulfonamide,4-dodecyloxybenzenesulfonamide, and2-octyloxy-5-tert-octylbenzenesulfonamide, alkoxycarbonyl group such asethoxycarbonyl, dodecyloxycarbonyl, and hexadecyloxycarbonyl, carbamoylgroup such as N-phenylcarbamoyl, N-ethylcarbamoyl, N-dodecylcarbamoyl,N-(2-dodecyloxyethyl)carbamoyl, andN-[3-(2,4-di-tert-pentylphenoxy)propyl]carbamoyl, sulfamoyl group suchas N,N-diethylsulfamoyl, N-ethyl-N-(2-dodecyloxyethyl)sulfamoyl, andN-[3-(2,4-di-tert-pentylphenoxy)propylzsulfamoyl, alkylthio group suchas ethylthio, dodecylthio, octadecyl, and3-(2,2-di-tert-phenoxy)propylthio, or sulfonyl group such asmethanesulfonyl, tetradecanesulfonyl, i-octadecanesulfonyl, andbenzenesulfonyl.

Referring in detail to R₂₇,R₂₇ represents an alkyl group preferablycontaining 1 to 22 carbon atoms such as methyl, ethyl, n-hexyl,n-dodecyl, t-butyl, 1,1,3,3-tetramethylbutyl, and2-(2,4-di-tert-amylphenoxy) ethyl, alkoxy group preferably containing 1to 22 carbon atoms such as methoxy, ethoxy, n-butoxy, n-octyloxy,2-ethylhexyloxy, n-dodecyloxy, n-hexadecyloxy, 2-ethoxyethoxy,2-dodecyloxyethoxy, 2-methanesulfonylethoxy,2-methanesulfonamide,3-(N-2-hydroxyethylsulfamoyl)proppoxy, and2-(N-2-methoxyethylcarbonyl)ethoxy, or aryloxy group preferablycontaining 6 to 32 carbon atoms such as phenoxy, 4-chlorophenoxy,2,4-dichlorophenoxy, 4-methoxyphenoxy, 4-dodecyloxyphenoxy, and3,4-methylenedioxyphenoxy. Referring in detail to R₂₉, R₂₉ represents ahydrogen atom, halogen atom such as fluorine atom, chlorine atom, andbromine atom, hydroxy group, alkyl group, alkoxy group, or aryl group.Such alkyl and alkoxy groups each preferably contain 1 to 22 carbonatoms as defined in R₂₇. Such an aryl group represents an aryl grouppreferably containing 6 to 32 carbon atoms such as phenyl,2,4-dichlorophenyl, 4-methoxyphenyl, 4-dodecyloxyphenyl,2,4-di-tert-amylphenoxy, 4-tert-octylphenyl, and4-(2-ethylhexaneamide)phenyl.

Referring in detail to R₂₈, R₂₈ represents a substituted orunsubstituted amino group such as N-alkylamino group, N,N-dialkylaminogroup, N-anilino group, N-alkyl-N-arylamino group, and heterocyclicamino group (e.g., N-butylamino, N,N-diethylamino,N-[2-(2,4-di-tert-amylphenoxy)ethyl]amino, N,N-dibutylamino,N-piperidino, N,N-bis-(2-dodecyloxyethyl)amino, N-cyclohexylamino,N,N-di-hexylamino, N-phenylamino, 2,4-di-tert-amylphenylamino,N-(2-chloro-5-tetradecaneamidephenyl)amino, N-methyl-N-phenylamino, andN-(2-pyridyl) amino, acylamino group such as acetamide, benzamide,tetradecaneamide, (2,4-di-tert-amylphenoxy)acetamide,2-chloro-benzamide, 3-pentadecylbenzamide,2-(2-methanesulfonamidephenoxy)dodecaneamide, and2-(2-chlorophenoxy)tetradecaneamide, ureide group such as methylureide,phenylureide, and 4-cyanophenylureide, alkoxycarbonylamino group such asmethoxycarbonylamino, dodecyloxycarbonylamino, and2-ethylhexyloxycarbonylamino, imide group such as N-succinimide,N-phthalimide, N-hydantoinyl, 5,5-dimethyl-2,4-dioxooxazole-3-il, andN-(3-octadecenyl)succimide, sulfonamide group such asmethanesulfonamide, octanesulfonamide, benzenesulfonamide,4-chlorobenzenesulfonamide, 4-dodecylbenznesulfonamide,N-methyl-N-benzenesulfonamide, 4-dodecyloxybenzenesulfonamide, andhexadecanesulfonamide, sulfamoylamino group such asN-octylsulfamoylamino, N,N-dipropylsulfamoylamino,N-ethyl-N-phenylsulfamoylamino, and N-(4-butyloxy)sulfamoylamino,alkoxycarbonyl group such as methoxycarbonyl, butoxycarbonyl,dodecyloxycarbonyl, and benzyloxycarbonyl, carbamoyl group such asN-octylcarbamoyl, N,N-dibutylcarbamoyl, N-phenylcarbamoyl, andN-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl, acyl group such asacetyl, benzoyl, hexanoyl, 2-ethylhexanoyl, and 2-chlorobenzoyl, cyanogroup, or alkylthio group such as dodecylthio, 2-ethylhexylthio,benzylthio, 2-oxocyclohexylthio, 2-(ethyltetradecanoate)thio,2-(dodecylhexanoate)thio, 3-phenoxypropylthio, and2-dodecanesulfonylethylthio.

Particularly preferred among compounds represented by the generalformula (Cp-II) is a compound wherein R₂₁ represents a hydrogen atom,R₂₂ represents a halogen atom, R₂₇ represents a C₁₋₂₂ alkoxy group, m₁and m₂ each represent an integer of 1, and m₃ represents 0.

Substituents for the general formula (Cp-III) will be described indetail hereinafter.

R₂₄ represents a hydrogen atom, halogen atom, alkyl group, aryl group,heterocyclic group, cyano group, alkoxy group, aryloxy group,heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxygroup, sulfonyloxy group, acylamino group, anilino group, ureide group,imide group, sulfamoylamino group, carbamoylamino group, alkylthiogroup, arylthio group, heterocyclic thio group, alkoxycarbonylaminogroup, aryloxycarbonylamino group, sulfonamide group, carbamoyl group,acyl group, sulfamoyl group, sulfonyl group, sulfinyl group,alkoxycarbonyl group, or aryloxycarbonyl group. Referring further tothese substituents, R₂₄ represents a hydrogen atom, halogen atom such aschlorine atom, and bromine atom, alkyl group such as methyl, propyl,isopropyl, t-butyl, trifluoromethyl, tridecyl,3-(2,4-di-amylphenoxy)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl,2-hexylsulfonyl-ethyl, 3-(2-butoxy-5-t-hexylphenylsulfonyl)propyl,cyclopentel, and benzyl, aryl group such as phenyl, 4-t-butylphenyl,2,4-di-t-amylphenyl, and 4-tetradecaneamidephenyl, heterocyclic groupsuch as 2-furyl, 2-chenyl, 2-pyrimidinyl, and 2-benzothiazolyl, cyanogroup, alkoxy group such as methoxy, ethoxy, 2-methoxyethoxy,2-dodecyloxyethoxy, 2-phenoxyethoxy, and 2-methanesulfonylehtoxy,aryloxy group such as phenoxy, 2-methylphenoxy, 2-methoxyphenoxy, and4-t-butylphenoxy, heterocyclic oxy group such as 2-benzimidazolyloxy,acyloxy group such as acetoxy, and hexadecanoiloxy, carbamoyloxy groupsuch as N-phenylcarbamoyloxy, and N-ethylcarbamoyloxy, silyloxy groupsuch as trimethylsilyloxy, sulfonyloxy group such as dodecylsulfonyloxy,acylamino group such as acetamide, benzamide, tetradecaneamide,α-(2,4-di-t-amylphenoxy) butylamide,γ-(3-t-butyl-4-hydroxyphenoxy)butylamide, andα-[4-(4-hydroxyphenylsulfonyl)phenoxyl]decaneamide, anilino group suchas phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneamideanilino,2-chloro-5 -dodecyloxycarbonylanilino, N-acetylanilino, and2-chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)dodecaneamide]anilino, ureidegroup such as phenylureide, methylureide, and N,N-di-butylureide, imidegroup such as N-succinimide, 3-benzylhydantoinyl, and4-(2-ethylhexanoilamino)phthalimide, sulfamoylamino group such asN,N-dipropylsulfamoylamino, and N-methyl-N-decylsulfamoyl, alkylthiogroup such as methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,3-phenoxypropylthio, and 3-(4-t-butylphenoxy) propylthio, arylthio groupsuch as phenylthio, 2-butoxy-5-t-octylphenylthio,2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,2-carboxyphenylthio, and 4-tetradecaneamidephenylthio, heterocyclic thiogroup such as 2-benzothiazolylthio, alkoxycarbonylamino group such asmethoxycarbonylamino, and tetradecyloxycarbonylamino,aryloxycarbonylamino group such as phenoxycarbonylamino, and2,4-di-tert-butylphenoxycarbonylamino, sulfonamide group such asmethanesulfonamide, hexadecanesulfonamide, benznesulfonamide,p-toluenesulfonamide, octadecanesulfonamide, and2-methyloxy-5-t-butylbenzenesulfonamide, carbamoyl group such asN-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl,and N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl, acyl group such asacetyl, (2,4-di-tert-amylphenoxy)acetyl, and benzoyl, sulfamoyl groupsuch as N-ethylsulfamoyl, N,N-dipropylsulfamoyl,N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, andN,N-diethylsulfamoyl, sulfonyl group such as methanesulfonyl,octanesulfonyl, benzenesulfonyl, toluenesulfonyl, and2-butoxy-5-tert-octylphenylsulfonyl, sulfinyl group such asoctanesulfinyl, dodecylsulfinyl, and phenylsulfinyl, alkoxycarbonylgroup such as methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, andoctanedecylcarbonyl, or aryloxycarbonyl group such as phenyloxycarbonyl,and 3-pentadecyloxycarbonyl.

In the general formula (Cp-III), Z₂₁ represents a hydrogen atom, orgroup capable of being released upon a reaction with an oxidationproduct of an aromatic primary amine color developing agent. Referringfurther to the releasable group represented by Z₂₁, examples of thereleasable group include halogen atom such as fluorine atom, chlorineatom, and bromine atom, alkoxy group such as dodecyloxy,dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy,and methanesulfonyloxy, aryloxy group such as 4-methylphenoxy,4-tert-butylphenoxy, 4-methoxyphenoxy, 4-methanesulfonylphenoxy, and4-(4-benzyloxyphenylsulfonyl)phenoxy, acyloxy group such as acetoxy,tetradecanoyloxy, and benzoyloxy, sulfonyloxy group such asmethanesulfonyloxy, and toluenesulfonyloxy, amide group such asdichloroacetylamino, methanesulfonylamino, and triphonylphosphonamide,alkoxycarbonyloxy group such as ethoxycarbonyloxy, andbenzyloxycarbonyloxy, aryloxycarbonyl group such as phenoxycarbonyloxy,aliphatic or aromatic thio group such as phenylthio, dodecylthio,benzylthio, 2-butoxy-5-tert-octylphenylthio, 2,5-di-octyloxyphenylthio,2-(2-ethoxy)-5-tert-octylphenylthio, and tetrazolylthio, imide groupsuch as succinimide, hydantoinyl, 2,4-dioxooxazolidine-3-il, and3-benzyl-4-ethoxyhydantoin-1-il, N-heterocyclic ring such as1-pyrazolyl, 1-benzotriazolyl, and 5-chloro-1,2,4-triazole-1-il, andaromatic azo group such as phenylazo. These releasable groups maycontain photographically useful groups.

In the general formula (Cp-III), R₂₄ or Z₂₁ may form a dimer or higherpolymer.

Particularly preferred among compounds represented by the generalformula (Cp-III) is a compound represented by the general formula(Cp-IV) or (Cp-V): ##STR11## wherein R₂₄ and Z₂₁ have the same meaningas defined in the general formula (Cp-III); and R₂₅ has the same meaningas R₂₄, with the proviso that R₂₄ and R₂₅ may be the same or different.

Particularly preferred among these compounds are those represented bythe general formula (Cp-V).

As typical yellow couplers used in the present invention, oil protectedacylacetamide type couplers are exemplified. Specific examples thereofare described in U.S. Pat. Nos. 2,407,210, 2,875,057, 3,265,506, etc. Inthe present invention, 2-equivalent yellow couplers are preferablyemployed and typical examples thereof include yellow couplers of theoxygen atom releasing type as described in U.S. Pat. Nos. 3,408,194,3,447,928, 3,933,501, 4,022,620, etc., and yellow couplers of nitrogenatom releasing type as described in Japanese Patent Publication No.10739/83, U.S. Pat. Nos. 4,401,752 and 4,326,024, Research Disclosure,No. 18053 (April, 1979), British Patent 1,425,020, West German PatentApplication (OLS) Nos. 2,219,917, 2,261,361, 2,329,587, 2,433,812, etc.α-Pivaloylacetanilide type couplers are characterized by excellentfastness, particularly light fastness of dyes formed therefrom, andα-benzoylacetanilide type couplers are characterized by providing highcolor density.

More preferable yellow coupler which may be used in the presentinvention is a yellow coupler (Cp-IV) as set forth below. ##STR12##wherein R₁₁ represents substituted or unsubstituted N-phenyl carbamoylgroup; and Z₁₁ represents a group which may be released when the couplerreacts with an oxidation products of an aromatic primary amine colordeveloping agent.

In general formula (Cp-VI), substituents of a phenyl group inN-phenylcarbamoyl group represented by R₁₁ include an aliphatic group(such as methyl, allyl, cyclopentyl), a heterocycryl group (such as2-pyridyl, 2-imidazaryl, 2-fryl, 6-quinoryl), an aliphatic oxy group(such as methoxy, 2-methoxyethoxy, 2-propenyloxy), an aromatic oxy group(such as 2,4-di-tert-amylphenoxy, 4-cyanophenoxy, 2-chlorophenoxy), anacyl group (such as an acetyl, benzoyl), an ester group (such as abutyoxycarbonyl, a hexadecyloxycarbonyl, phenoxycarbonyl, dodecyloxy,carbonylmethoxycarbonyl, acetoxy, benzoyloxy, tetradecyloxysulfonyl,hexadecanesulfonyl, etc.), an amido group (such as acetylamino,dodecanesulfoneamido, α-(2,4-di-tert-pentylphenoxy)butanamido,γ-(2,4-di-tert-pentylphenoxy)butanamido, N-tetradexylcarbamoyl,N,N-dihexylcarbamoyl, N-butansulfamoyl, N-methyl-N-tetradecahsulfamoyl),an imido group (such as succinimido, N-hidantonyl,3-hexadecenylsuccinimido), an ureido group (such as phenylureido,N,N-dimethylureido, N-(3-(2,4-di-tert-pentylphenoxy)propyl)ureido), analiphatic or aromatic sulfonyl group (such as methanesulfonyl,phenylsulfonyl, dodecanesulfonyl, 2-butoxy-5-tert-octylbenzenesulfonyl),an aliphatic or aromatic thio group (such as phenylthio, ethylthio,hexadecylthio, 4-(2,4-di-tert-phenoxyacetoamido)benzylthio), a hydroxygroup, a sulfonic acid group, a halogen atom (such as fluorine,chlorine, bromine) and the like. When two or more of substituent groupare present, these may be the same or different.

In general formula (Cp-VI), Z₁₁ represents a coupling rease group whichincludes a halogen atom (such as fluorine, chlorine, bromine), an alkoxygroup (such as dodesyloxy, dodesyloxycarbonylmethoxy,methoxycarbamoylmethoxy, carboxypropyloxy, methanesulfonyloxy), anaryloxy group (such as 4-methylphenoxy, 4-tert-butylphenoxy,4-methanesulfonylphenoxy, 4-(4-benzyloxyphenylsulfonyl)phenoxy,4-methoxycarbonylphenoxy), an acyloxy group (such as acetoxy,tetradecanoyloxy, benzoyloxy), sulfonyloxy group (such asmethanesulfonyloxy, toluenesulfonyloxy), an amido group (such asdichloroacetylamino, methanesulfonylamino), an alkoxycarbonyloxy group(such as ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (such as phenoxycarbonyloxy), an aliphatic or aromaticthio group (such as phenylthio, dodesylthio, benzylthio,2-butoxy-5-tert-octylphenylthio,2-(2-ethoxyethoxy)-5-tert-octylphenylthio, tetrazalylthio), an imidogroup (such as succinimido, hydantonyl, 2,4-dioxazolidyne-3-yl,3-benzyl-4-ethoxyhydantoin-1-yl, 3-benzylhydantoin-1-yl,1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidine-4-yl,3-benzyl-4-ethoxyhydantoin-1-yl), an heterocyclic ring (such as1-pyrazolyl, 1-benzotriazolyl, 5-chloro-1,2,4-triazole-1-yl), anaromatic azo group (such as phenylazo) and the like.

These releasable groups in the compound may contain a photographicallyuseful group.

In general formula (Cp-VI), R₁₁ and Z₁₁ may form divalent or more highervalent groups.

The amount of the coupler used in the present invention is generallyfrom 0.01 to 2 mols, preferably from 0.1 to 1.0 mol per mol of silverhalide present in the silver halide emulsion layer.

Preferred specific examples of cyan couplers which can be used in thepresent invention are set forth below, but the present invention shouldnot be construed as being limited thereto. ##STR13##

In the following, the ratio of x and y or x, y and z is by weight.##STR14##

Specific examples of oil-soluble magenta and yellow couplers which canbe used in the present invention are set forth below, but the presentinvention should not be construed as being limited thereto. ##STR15##

In the following, the water-immiscible coupler solvents having a highboiling point which can be employed in the present invention aredescribed in detail.

Of the water-immiscible coupler solvents used in the present invention,any compound which has a melting point of not more than 100° C. and aboiling point of not less than 140° C., and is water-immiscible and agood solvent for the coupler can be employed as the coupler solventhaving a high boiling point according to the present invention. Themelting point of the coupler solvent having a high boiling point ispreferably not more than 80° C. The boiling point of the coupler solventhaving a high boiling point is preferably not less than 160° C. and morepreferably not less than 170° C.

When the melting point of the coupler solvent exceeds about 100° C.,crystallization of couplers is apt to occur and color forming abilitytends to become poor.

Further, when the boiling point of the coupler solvent is lower thanabout 140° C., such a coupler solvent is hard to be maintained in thephotographic emulsion layer as droplets together with the coupler andthe polymer according to the present invention because it easilyevaporates during coating and drying the photographic emulsion. As aresult, it is difficult to achieve the effect of the present invention.

Moreover, when using a coupler solvent which is miscible with water, thecouplers, etc., are apt to move to other photographic layers or diffuseinto the processing solution during coating of the photographic emulsionlayer or photographic processing of the photographic light-sensitivematerial obtained by coating and drying. These phenomena cause theformation of color mixing and fog and cause a decrease in maximum colordensity.

In the present invention, the amount of the coupler solvent having ahigh boiling point can be varied in a wide range, depending on the kindsand amounts of coupler and the polymer to be employed. However, theratio of coupler solvent having a high boiling point/coupler by weightis preferably from 0.05 to 20, and more preferably from 0.1 to 10. Also,the ratio of coupler solvent having a high boiling point/polymer byweight is preferably from 0.02 to 40, and more preferably from 0.50 to20. Further, a coupler solvent having a high boiling point can beemployed individually or in a combination of two or more thereof.

Of the compounds represented by the general formulae (III) to (VIII),those represented by the general formulae(III), (IV) and (VIII) arepreferred. (III) and (IV), a compound of formula (IX) is most preferred.##STR16## wherein n is an integer of from 3 to 15; and W₇ represents asubstituted or unsubstituted alkyl group having 4 to 15 carbon atoms.

Specific examples of the substituted or unsubstituted alkyl, cycloalkyl,alkenyl, aryl or heterocyclic groups represented by W₁ to W₆ in formulae(III) to (VIII) are the same as the groups illustrated with respect tothe general formula (Cp-I) and (Cp-II). Also, an alkyl group may bebonded to an epoxy group.

Specific examples of the coupler solvents having a high boiling pointwhich can be used in the present invention are set forth below, but thepresent invention should not be construed as being limited thereto.##STR17##

The dispersion of oleophilic fine particles containing the coupler, thecoupler solvent having a high boiling point and the polymer used in thepresent invention can be prepared in the following manner.

The polymer according to the present invention may be synthesized by asolution polymerization method, an emulsion polymerization method, asuspension polymerization method, etc., and is not cross-linked (i.e., alinear polymer). The coupler solvent has a high boiling point and thecoupler is completely dissolved in an auxiliary organic solvent. Thesolution is dispersed in water, preferably in an aqueous solution of ahydrophilic colloid, and more preferably in an aqueous solution ofgelatin with the assistance of a dispersant using ultrasonic agitation,a colloid mill, etc., to form fine particles. Then, the dispersion ismixed with a silver halide emulsion. Alternatively, water or an aqueoussolution of a hydrophilic colloid such as an aqueous solution ofgelatin, etc., is added to an auxiliary organic solvent containing adispersant such as a surface active agent, etc., the polymer accordingto the present invention, the coupler solvent having a high boilingpoint and the coupler to prepare an oil in water type dispersionaccompanied by phase inversion.

Further, the dispersion may be mixed with a photographic emulsion afterremoving the auxiliary organic solvent therefrom by distillation, noodlewashing, ultrafiltration, etc. The term "auxiliary organic solvent" asused herein means an organic solvent which is useful in forming anemulsified dispersion which is finally removed substantially from thephotographic light-sensitive material during the drying step aftercoating or by the above-described method, and which is an organicsolvent having a low boiling point or a solvent having a certain extentof solubility in water and removable by washing with water, etc.Specific examples of auxiliary organic solvents include a lower alkylacetate such as ethyl acetate, butyl acetate, etc., ethyl propionate,sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone,β-ethoxyethyl acetate, methyl cellosolve acetate, methylcarbitolacetate, methylcarbitol propionate, cyclohexanone, etc.

Further, an organic solvent which is completely miscible with water, forexample, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, etc.,may be partially employed together with the auxiliary organic solvent,if desired.

Moreover, these organic solvents can be used in a mixture of two or morethereof.

The average particle diameter of the oleophilic fine particlesthus-obtained is preferably from 0.04 μm to 2 μm and more preferablyfrom 0.06 μm to 0.4 μm. The particle diameter of the oleophilic fineparticles can be measured by a suitable apparatus such as Nanosizermanufactured by the Coal-Tar Limited in England, etc.

Into the oleophilic fine particles used in the present invention,various kinds of photographic hydrophobic substances can beincorporated. Suitable examples of such photographic hydrophobicsubstances include colored couplers, non-color forming couplers,developing agents, developing agent precursors, development inhibitorprecursor, ultraviolet ray absorbing agents, development accelerators,gradation controlling agents such as hydroquinones, etc., dyes, dyereleasers, antioxidants, fluorescent brightening agents, color fadingpreventing agents, etc. Two or more of these hydrophobic substances canbe used together.

Further, the compounds represented by the general formulae (A), (B) and(C) described below are particularly useful as photographic hydrophobicsubstances for incorporation into the oleophilic fine particlescomprising the coupler, the coupler solvent having a high boiling pointand the polymer according to the present invention, since it can furtherincrease color forming ability and prevent fading according to thepresent invention. ##STR18## wherein A represents a divalent electronwithdrawing group; R₁ represents a substituted or unsubstituted alkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted aryloxygroup, a substituted or unsubstituted alkylamino group, a substituted orunsubstituted anilino group or a substituted or unsubstitutedheterocyclic group; represents an integer of 1 or 2; R₂ represents asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedalkoxy group, a hydroxy group, or a halogen atom; m represents aninteger from 0 to 4; and Q, if present, represents a benzene ring or ahetero ring condensed with the phenol ring. ##STR19## wherein R₃, R₄ andR₅ each represents a hydrogen atom, a halogen atom, a nitro group, ahydroxy group, a substituted or unsubstituted alkyl group, a substitutedor unsubstituted alkoxy group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted aryloxy group or a substituted orunsubstituted acylamino group. ##STR20## wherein R₆ and R₇ eachrepresents a hydrogen atom, a substituted or unsubstituted alkyl group,a substituted or unsubstituted alkoxy group or a substituted orunsubstituted acyl group; X represents --CO-- or --COO--; and nrepresents an integer from 1 to 4.

Specific examples of the compounds represented by the general formulae(A), (B) and (C) are set forth below, but the present invention shouldnot be construed as being limited thereto. ##STR21##

Any silver halide, such as silver chloride, silver iodobromide, silverbromide, silver chlorobromide, silver chloroiodobromide, etc.,conventionally used in a silver halide emulsion can be employed in thesilver halide emulsion according to the present invention. Silver halidegrains may be coarse grains or fine grains. Grain size distribution maybe narrow or broad, but it is preferred to use a monodispersed emulsionhaving a percentage of grains greater than or less than the averagegrain size by 40% or more of not more than 15% and more preferably notmore than 10%.

Silver halide grains may have a regular crystal structure or anirregular crystal structure, such as a spherical structure, a tabularstructure, a twin structure, etc. Further, any crystal structure havinga various ratio of a [100]plane to a [111]plane may be employed. Thecrystal structure of silver halide grains may be uniform, composed ofdifferent halide compositions between the inner portion and the outerportion, or may have a layer structure. Moreover, the silver halidegrains may be those of the surface latent image type in which latentimages are formed mainly in the surface portion thereof or those of theinternal latent image type in which latent images are formed mainly inthe interior thereof. The silver halide emulsions can be those preparedby an acid process, a neutral process and an ammonia process. Further,silver halide grains prepared by a double jet process, a single jetprocess, a reverse mixing process, a conversion method, etc., can beemployed. It is also possible to use a mixture of two or more kinds ofsilver halide emulsions which are prepared separately.

Silver halide photographic emulsions comprising silver halide grainsdispersed in a binder can be subjected to chemical sensitization using achemical sensitizer. Chemical sensitizers which can be preferablyemployed individually or in a combination in the present inventionincludes noble metal sensitizers, sulfur sensitizers, seleniumsensitizers, and reducing sensitizers.

Noble metal sensitizers include gold compounds and ruthenium, rhodium,palladium, iridium, platinum compounds, etc.

Ammonium thiocyanate or sodium thiocyanate can be employed together withthe gold compound.

Sulfur sensitizers include active gelatin, a sulfur compound, etc.

Selenium sensitizers include an active or inactive selenium compound,etc.

Reducing sensitizers include a stannous salt, a polyamine, abisalkylaminosulfide, a silane compound, an iminoaminomethanesulfinicacid, a hydrazinium salt, a hydrazine derivative, etc.

In the color photographic light-sensitive material according to thepresent invention, it is preferred to appropriately provide a subsidiarylayer such as a protective layer, intermediate layer, a filter layer, anantihalation layer, a back layer, etc., in addition to the silver halideemulsion layer.

As the binder or the protective colloid for the photographic emulsionlayers or intermediate layers of the color photographic light-sensitivematerial according to the present invention, gelatin is advantageouslyused, but other hydrophilic colloids can be used.

For example, it is possible to use proteins such as gelatin derivatives,graft polymers of gelatin and other polymers, albumin, casein, etc.;saccharide derivatives including cellulose derivatives such ashydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate,etc., sodium alginate, starch derivatives, etc.; and various synthetichydrophilic high molecular substances such as homopolymers orcopolymers, for example, polyvinyl alcohol, polyvinyl alcoholsemiacetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylicacid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.

As gelatin, not only lime-processed gelatin, but also acid-processedgelatin and enzyme-processed gelatin as described in Bull. Soc. Sci.Phot. Japan, No. 16, page 30 (1966) may be used. Further, hydrolyzedproducts of gelatin or enzymatically decomposed products of gelatin canalso be used.

Into the silver halide emulsion layer and the subsidiary layer of thecolor photographic light-sensitive material of the present invention canbe incorporated various kinds of photographic additives. For example,antifogging agents, dye image fading preventing agents, colorcontamination preventing agents, fluorescent whitening agents,antistatic agents, hardening agents, surface active agents,plasticizers, wetting agents and ultraviolet ray absorbing agents, etc.,as described in Research Disclosure, No. 17643 can be employed whenneeded.

The silver halide color photographic material of the present inventioncan be produced by coating one or more silver halide emulsion layers andone or more subsidiary layers, each containing various photographicadditives as described above, if desired, on a support which has beensubjected to a corona discharge treatment, a flame treatment or anultraviolet irradiation treatment, etc., or on a support having asubbing layer or an intermediate layer. Examples of supports which canbe advantageously employed include baryta coated paper, polyethylenecoated paper, polypropylene type synthetic paper, a transparent support,for example, a glass plate, a polyester film such as a cellulosetriacetate film, a cellulose nitrate film, a polyethylene terephthalatefilm etc., a polyamide film, a polycarbonate film, a polystyrene film,etc., having a reflective layer or having incorporated therein areflective substance. A suitable support can be selected depending onthe purpose for which the photographic light-sensitive material is to beused.

In the present invention, photographic emulsion layers and otherconstituent layers can be coated on a support or other layers on asupport using various conventional coating methods. Examples of suchcoating methods include the dip coating method, the air doctor coatingmethod, the curtain coating method, the hopper coating method, etc.Further, the coating methods described in U.S. Pat. Nos. 2,761,791 and2,941,898, etc., in which two or more layers may be coated at the sametime if desired, may be used.

In the present invention, the position of each emulsion layer can be inany order which is appropriate. For example, the layers may be in theorder of blue-sensitive emulsion layer, green-sensitive emulsion layerand red-sensitive emulsion layer from the support side, or in the orderof red-sensitive emulsion layer, green-sensitive emulsion layer andblue-sensitive emulsion layer from the support side can be employed.

Further, an ultraviolet ray absorbing layer may be a layer adjacent toan emulsion layer farthest from the support, or, if desired, as a layeron the opposite side of the support. In the latter case, it isparticularly preferred to provide a layer substantially comprising onlygelatin as the uppermost layer.

The present invention is preferably applied to color photographiclight-sensitive materials for prints. When used for that purpose, thecolor photographic light-sensitive material is exposed through a colornegative photographic material having color images composed of couplingproducts and then subjected to color development processing.

The color developing solution used in the development of thelight-sensitive material of the present invention is preferably analkaline aqueous solution containing an aromatic primary amine colordeveloping agent as a main component: As such a color developing agentthere is effectively used an aminophenol compound. p-Phenylenediaminecompound is more preferably used as such a color developing agent.Typical examples of such a p-phenylenediamine compound include3-methyl-4-amino-N,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline,3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates,hydrochlorides, and p-toluenesulfonates thereof. These compounds may beused in combination depending on the purpose of application.

In general, the color developing solution contains a pH buffer such ascarbonate, borate, and phosphate of alkali metal, development inhibitoror fog inhibitor such as bromide, iodide, benzimidazoles,benzothiazoles, and mercapto compound, or the like. Other typicalexamples of compounds which can be optionally contained in the colordeveloping solution include various preservatives such as hydroxylamine,diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides,triethanolamine, catecholsulfonic acids, and triethylenediamine(1,4-diazabicyclo[2,2,2]octanes, organic solvents such asethyleneglycol, and diethyleneglycol, development accelerators such asbenzylalcohol, polyethyleneglycol, quaternary ammonium salts, andamines, dye forming couplers, competing couplers, fogging agents such assodium boron hydride, auxiliary developing agents such as1-phenyl-3-pyrazolidone, thickening agents, and various chelating agentssuch as aminopolycarboxylic acids, aminopolyphosphonic acids,alkylphosphonic acids, and phosphonocarboxylic acids. Typical examplesof such chelating agents include ethylenediaminetetraacetic acid,nitrilotriacetic acid, diethylenetriaminepentaacetic acid,cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,1-hydroxyethylidene-1,1-diphosphonic acid,nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid,ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.

If the reversal process is effected, the color development is normallyeffected after a black-and-white development. The solution to be used inthe black-and-white development process may comprise knownblack-and-white developing agents such as dihydroxybenzenes, e.g.,hydroquinone, 3-pyrazolidones, e.g., 1-phenyl-3-pyrazolidone, andaminophenols, e.g., N-methyl-p-aminophenol, singly or in combination.

In general, these color developing solutions and black-and-whitedeveloping solutions have a pH value of 9 to 12. The amount of thesedeveloping solutions to be filled up normally depends on the type ofcolor photographic light-sensitive materials to be processed. It isnormally in the range of 3 or less per 1 m₂ of light-sensitive material.If the bromide ion concentration of the solution to be filled up islowered, the amount of the solution to be filled up can be reduced to500 ml or less. In the case where the amount of the solution to befilled up is reduced, the evaporation and air oxidation of the solutionis preferably prevented by reducing the contact area of the processingbath with air. Alternatively, the amount of the solution to be filled upcan be reduced by a means for inhibiting the accumulation of bromideions in the developing solution.

The photographic emulsion layer which has been color developed isnormally subjected to bleach. The bleach may be effected simultaneouslywith or separately from fixing. (If the bleach is effectedsimultaneously with fixing, it is called blix.) In order to expedite theprocessing, the bleach may be followed by the blix. Alternatively, anyother processing steps may be optionally used. For example, a blix bathmade of two continuous tanks may be used. Furthermore, the blix may bepreceded by the fixing. Moreover, the blix may be followed by thebleach. As bleaching agent there can be used compounds of polyvalentmetals such as iron (III), cobalt (III), chromium (VI), and copper (II),peracids, quinones, and nitro compounds. Typical examples of bleachingagents which can be used in the present invention include ferricyanides,dichromates, organic complex salts of iron (III) or cobalt (III) Withethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid,or other aminopolycarboxylic acids, or citric acid, tartaric acid, ormalic acid, persulfates, bromates, permanganates, and nitrobenzenes.Preferred among these bleaching agents are ethylenediaminetetraaceticacid-iron (III) complex salts and other aminopolycarboxylic acid-iron(III) complex salts, and persulfates in view of rapidness of processingand prevention of environmental pollution. Furthermore,aminopolycarboxylic acid-iron (III) complex salts are also useful forbleaching bath and blix bath in particular. The bleaching solution orblix solution comprising such aminopolycarboxylic acid-iron (III)complex salts normally has a pH of 5.5 to 8. In order to expedite theprocessing, the bleaching solution or blix solution may be lower in pHvalue.

The bleaching solution, blix solution and their prebaths may optionallycomprise any suitable bleach accelerators. Specific examples of usefulbleach accelerators include compounds containing mercapto groups ordisulfide groups as described in U.S. Pat. No. 3,893,858, West GermanPatent Nos. 1,290,812, and 2,059,988, Japanese Patent Application (OPI)Nos. 32,736/78, 57,831/78, 37,418/78, 72,623/78, 95,631/78, 104,232/78,124,424/78, 141,623/78, and 28,426/78, and Research Disclosure No.17,129 (July 1978), thiazolidine derivatives as described in JapanesePatent Application (OPI) No. 140,129/75, thiourea derivatives asdescribed in Japanese Patent Publication No. 8,506/70, Japanese PatentApplication (OPI) Nos. 20,832/77, and 32,735/78, and U.S. Pat. No.3,706,561, iodides as described in West German Patent No. 1,127,715, andJapanese Patent Application (OPI) No. 16,235/83, polyoxyethylenecompounds as described in West German Patent Nos. 966,410, and2,748,430, polyamine compounds as described in Japanese PatentPublication No. 8836/70, compounds as described in Japanese PatentApplication (OPI) Nos. 42,434/74, 59,644/74, 94,927/78, 35,727/79,26,506/80, and 163,940/83, and bromides. Preferred among these compoundsare compounds containing mercapto groups or disulfide groups in view ofbleach accelerating effect. Particularly preferred among these compoundsare compounds as described in U.S. Pat. No. 3,893,858, West GermanPatent No. 1,290,812, and Japanese Patent Application (OPI) No.95,630/78. Furthermore, compounds as described in U.S. Pat. No.4,552,834 can be preferably used. These bleach accelerators may beincorporated in the light-sensitive material. These bleach acceleratorsare useful particularly when color light-sensitive materials forphotographing are subjected to blix.

As fixing agents there may be used thiosulfates, thiocyanates, thioethercompounds, thioureas, and iodides in a large amount. In general,thiosulfates are commonly used. In particular, ammonium thiosulfate canbe most widely used. As preservatives for blix solution there may bepreferably used sulfites, bisulfites, or carbonylbisulfurous acidaddition products.

In general, the silver halide color photographic material of the presentinvention is subjected to washing and/or stabilizing after desilvering.The amount of water to be used in washing can be widely determineddepending on the properties of the light-sensitive material (given byelements used such as coupler), purpose, temperature of water to be usedwashing, number of washing tanks (number of stages), solution supplementsystem in which countercurrent, forwardcurrent, or the like is used, orother various conditions. In particular, the relationship between thenumber of washing tanks and the amount of water to be used in themultistage countercurrent system can be determined by a method asdescribed in Journal of the Society of Motion Picture and TelevisionEngineers (Vol. 64, pp. 248-253, May 1955).

The multistage countercurrent system described in the above citedreference enables saving of a large amount of wash water. However, thissystem is disadvantageous in that a longer retention of water in thetanks causes propagation of bacteria which will produce floating mattersthat can attach to the light-sensitive material. In the processing ofthe present color photographic light-sensitive material, a method asdescribed in Japanese Patent Application No. 131,632/76 which comprisesreducing calcium or magnesium ions can be extremely effectively used toeliminate such a disadvantage. Alternatively, isothiazolone compoundsand cyabendazoles as described in Japanese Patent Application (OPI) No.8,542/82, chlorine germicides such as chlorinated sodium isocyanurate,benzotriazole, or other germicides as described in "Anti-bacterial andAnti-funglal Chemistry" (edited by Hiroshi Horiguchi), "Technich forsterilization of microorganism" (edited by EISEI GIJUTSUKAI), and"Dictionary of Anti-bacterial and Anti-fungal Agents" (edited by NIPPONBOKIN BOBAI GAKKAI) may be used.

Wash water to be used in the processing of the light-sensitive materialof the present invention has a pH value of 4 to 9, preferably 5 to 8.The temperature of wash water and washing time can be similarly widelydetermined depending on the properties of the light-sensitive materialand the purpose. In general, these values are in the range of 15° to 45°C. for 20 seconds to 10 minutes, preferably 25° to 40° C. for 30 secondsto 5 minutes. Furthermore, the light-sensitive material of the presentinvention may be directly processed with a stabilizing solution insteadof wash water. In such a stabilizing process, any known methods asdescribed in Japanese Patent Application (OPI) Nos. 8,543/82, 14,834/83,and 220,345/85 can be used.

Alternatively, the above described washing may be optionally followed bya stabilizing process. For example, a stabilizing bath containingformalin and a surface active agent used as a final bath in theprocessing of color photographic light-sensitive material forphotographing can be used. This stabilizing bath may comprise variouschelating agents or anti-fungal agents.

The overflow solution given as wash water and/or stabilizing solution isfilled up can be reused in other processes such as desilvering process.

In order to simplify and expedite the processing, the silver halidecolor photographic material of the present invention may comprise acolor developing agent incorporated therein. The incorporation of such acolor developing agent in the light-sensitive material is preferablyeffected by the use of various precursors of color developing agent.Examples of such color developing agent precursors include indoanilinecompounds as described in U.S. pat. No. 3,342,597, Schiff base typecompounds as described in U.S. Pat. No. 3,342,599, and ResearchDisclosure Nos. 14,850, and 15,159, aldol compounds as described inResearch Disclosure No. 13,924, metal complexes as described in U.S.Pat. No. 3,719,492, and urethane compounds as described in JapanesePatent Application (OPI) No. 135,628/78.

In order to accelerate color development, the silver halide colorlight-sensitive material of the present invention may optionallycomprise various 1-phenyl-3-pyrazolidones incorporated therein. Typicalexamples of such compounds are described in Japanese Patent Application(OPI) Nos. 64,339/81, 144,547/82, and 115,438/83.

In the present invention, various processing solutions may be used at atemperature of 10° to 50° C. The standard temperature range is normallybetween 33° C. and 38° C. A higher temperature can be used to acceleratethe processing, reducing the processing time. On the contrary, a lowertemperature can be used to improve the image quality or the stability ofthe processing solution. In order to save silver in the light-sensitivematerial, a processing method using a cobalt intensification or hydrogenperoxide as described in West German Patent No. 2,226,770 or U.S. Pat.No. 3,764,499 may be employed.

The present invention is explained in greater detail with reference tothe following examples, but the present invention should not beconstrued as being limited thereto.

EXAMPLE (1)

Sample (A) according to the present invention was prepared in thefollowing manner.

A solution composed of 10 g of Polymer (P-3) according to the presentinvention, 10 g of Coupler (C-1), 6 g of Coupler Solvent (S-16) and 50ml of ethyl acetate was heated to 50° C. and added to 100 ml of anaqueous solution containing 15 g of gelatin and 1.0 g of sodiumdodecylbenzenesulfonate, and the mixture was stirred using a high speedstirrer (Homogenizer manufactured by Nippon Seiki Seisakusho) to obtaina finely dispersed emulsified dispersion.

The emulsified dispersion thus obtained was mixed with a silverchlorobromide photographic emulsion (silver chloride 98 mol%), pH of themixture was adjusted to 6.0, and the resulting mixture was coated on apaper support, both surfaces of which were laminated with polyethyleneto prepare Sample (A) according to the present invention having thelayer structure and the composition of main components shown in Table 1below. As a gelatin hardener, 4,6-dichloro-2-hydroxy-s-trizine sodiumsalt was used.

                  TABLE 1                                                         ______________________________________                                        Third Layer: Protective Layer                                                 Gelatin                 1,000  mg/m.sup.2                                     Second Layer: Ultraviolet Light Absorbing                                     Layer                                                                         Ultraviolet Light Absorbing Agent (*1)                                                                600    mg/m.sup.2                                     Ultraviolet Light Absorbing Agent                                                                     300    mg/m.sup.2                                     Solvent (*2)                                                                  Gelatin                 800    mg/m.sup.2                                     First Layer: Emulsion Layer                                                   Silver chlorobromide emulsion                                                                         300    mg/m.sup.2                                     (silver chloride: 98 mol %)                                                                           (as silver)                                           Coupler (C-1)           1.01   mmol/m.sup.2                                   Coupler Solvent (S-16)  300    mg/m.sup.2                                     Polymer (P-3)           500    mg/m.sup.2                                     Gelatin                 1,250  mg/m.sup.2                                     Support:                                                                      Paper support, both surfaces of which were                                    laminated with polyethylene                                                   ______________________________________                                         (*1) 2(2-Hydroxy-3-sec-butyl-5-tert-butylphenyl)-benzotriazole                (*2) Dibutyl phthalate                                                   

In the same manner as described above, Samples (B) to (Z) according tothe present invention and Samples (1) to (6) for comparison wereprepared. The kind and amount of polymer and the kind of coupler usedare shown in Table 2 and the other components are the same as thosedescribed for Sample (A) shown in Table 1.

Further, the average particle sizes of the oleophilic fine particlescomposed of coupler, polymer and coupler solvent having a high boilingpoint used in Samples (A) to (Z) according to the present invention andthe average particle sizes of oleophilic fine particles composed of thecoupler and the coupler solvent having a high boiling point used inSamples (1) to (6) for comparison was in the range of from 0.10 μm to0.17 μm.

These samples were subjected to continuous gradation exposure through anoptical wedge for sensitometry and then processed as described below.

    ______________________________________                                        1.    Color Development                                                                           35° C.                                                                             45 sec                                        2.    Bleach-Fixing 35° C.                                                                             1 min 00 sec                                  3.    Washing with Water                                                                          25 to 30° C.                                                                       2 min 30 sec                                  ______________________________________                                    

The composition of each processing solution used for the above colordevelopment processing steps was as follows.

    ______________________________________                                        Color Developing Solution:                                                    Water                     800    ml                                           Ethylenediaminetetraacetic Acid                                                                         1.0    g                                            Sodium Sulfite            0.2    g                                            N,N-Diethylhydroxylamine  4.2    g                                            Potassium Bromide         0.01   g                                            Sodium Chloride           1.5    g                                            Triethanolamine           8.0    g                                            Potassium Carbonate       30     g                                            N-Ethyl-N-(β-methanesulfonamidoethyl)-                                                             4.5    g                                            3-methyl-4-aminoaniline Sulfate                                               4,4'-Diaminostilbene Type Fluorescent                                                                   2.0    g                                            Whitening Agent (Whitex 4 manufactured                                        by Sumitomo Chemical Co., Ltd.)                                               Water to make             1,000  ml                                           Adjusted pH to 10.25 with KOH                                                 Bleach-Fixing Solution:                                                       Ammonium Thiosulfate (54% by weight                                                                     150    ml                                           aqueous solution)                                                             Na.sub.2 SO.sub.3         15     g                                            NH.sub.4 [Fe(III) (EDTA)] 55     g                                            EDTA·2Na         4      g                                            Glacial Acetic Acid       8.61   g                                            Water to make             1,000  ml                                                                     pH     5.4                                          Rinse Solution:                                                               EDTA·2Na·2H.sub.2 O                                                                   0.4    g                                            Water to make             1,000  ml                                                                     pH     7.0                                          ______________________________________                                    

After processing, the samples were subjected to the following tests inorder to evaluate their light fastness, heat fastness and fastness tocombined high humidity and heat. More specifically, each of the sampleswas stored in a dark place at 100° C. for 5 days, and at 60° C. for 9months stored in a dark place at 80° C. and 70% RH for 12 days, and at60° C. and 70% RH for 3 months or irradiated to light in a fluorescentlap Fade-Ometer (30,000 lux) for 5 months. Then, the rate of decrease inimage density in the area on the photographic material having an initialdensity of 1.5 was determined wherein an initial density was 1.0 in alight fastness test. The results thus obtained are shown in Table 2.

    ______________________________________                                        Color Developing Solution:                                                    Water                     800    ml                                           Ethylenediaminetetraacetic Acid                                                                         1.0    g                                            Sodium Sulfite            0.2    g                                            N,N-Diethylhydroxylamine  4.2    g                                            Potassium Bromide         0.01   g                                            Sodium Chloride           1.5    g                                            Triethanolamine           8.0    g                                            Potassium Carbonate       30     g                                            N-Ethyl-N-(β-methanesulfonamidoethyl)-                                                             4.5    g                                            3-methyl-4-aminoaniline Sulfate                                               4,4'-Diaminostilbene Type Fluorescent                                                                   2.0    g                                            Whitening Agent (Whitex 4 manufactured                                        by Sumitomo Chemical Co., Ltd.)                                               Water to make             1,000  ml                                           Adjusted pH to 10.25 with KOH                                                 Bleach-Fixing Solution:                                                       Ammonium Thiosulfate (54% by weight                                                                     150    ml                                           aqueous solution)                                                             Na.sub.2 SO.sub.3         15     g                                            NH.sub.4 [Fe(III) (EDTA)] 55     g                                            EDTA·2Na         4      g                                            Glacial Acetic Acid       8.61   g                                            Water to make             1,000  ml                                                                     pH     5.4                                          Rinse Solution:                                                               EDTA·2Na·2H.sub.2 O                                                                   0.4    g                                            Water to make             1,000  ml                                                                     pH     7.0                                          ______________________________________                                    

After processing, the samples were subjected to the following tests inorder to evaluate their light fastness, heat fastness and fastness tocombined high humidity and heat. More specifically, each of the sampleswas stored in a dark place at 100° C. for 5 days, and at 60° C. for 9months stored in a dark place at 80° C. and 70% RH for 12 days, and at60° C. and 70% RH for 3 months or irradiated to light in a fluorescentlap Fade-Ometer (30,000 lux) for 5 months. Then, the rate of decrease inimage density in the area on the photographic material having an initialdensity of 1.5 was determined wherein an initial density was 1.0 in alight fastness test. The results thus obtained are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                                                      Light Fading                         Polymer                                  Fluorescent                                Amount                                                                              Dark Fading                  Lamp                                 Compound                                                                            used  >100° C.                                                                    >60° C.                                                                      >80° C., 70% RH                                                                 >60° C., 70%                                                                    (30,000 Lux)                Sample                                                                            Coupler                                                                            (Formula)                                                                           mg/m.sup.2                                                                          5 Days                                                                             9 Months                                                                            12 Days  3 Months 5 Months                    __________________________________________________________________________    A   C-1  P-3     500 37%  31%   30%      29%      38% Comparison              B   "    P-3   1,000 28%  22%   19%      18%      32% Comparison              C   "    P-8   1,000 27%  42%   21%      27%      34% Comparison              D   "    P-14  1,000 29%  46%   22%      24%      35% Comparison              E   "    P-57  1,000 21%  15%   13%      14%      24% Comparison              F   "    P-64  1,000 23%  15%   15%      14%      24% Comparison              G   "    P-65  1,000 21%  17%   14%      13%      25% Comparison              H   "    P-129 1,000 23%  21%   15%      14%      27% Comparison              I   C-2  P-64  1,000 11%   5%    7%       4%      30% Present Invention       J   C-3  P-3   1,000 15%  19%    9%       6%      36% Present Invention       K   "    P-8   1,000 16%  17%   10%      10%      40% Comparison              L   "    P-57    500 18%  10%   12%       9%      42% Present Invention       M   "    "     1,000 12%   6%    7%       4%      42% Present                 __________________________________________________________________________                                                      Invention                                                                        Fluorescent Lamp                   Polymer                                    (30,000 Lux)                             Amount                                                                              Discoloration in Dark          Discoloration                      Compound                                                                            used  >100° C.                                                                     >60° C.                                                                      >80° C., 70% RH                                                                 >60° C., 70%                                                                     under light              Sample                                                                            Coupler                                                                             (Formula)                                                                           mg/m.sup.2                                                                          5 Days                                                                              9 Months                                                                            12 Days  3 Months  5 Months                 __________________________________________________________________________    Present Invention                                                             N   C-3   P-64  1,000 13%    6%    8%       4%       32%                      O   "     P-129 1,000 14%    9%    8%       5%       33%                      P   C-11  P-3   1,000 22%   13%   15%      12%       28%                      Q   "     P-56  1,000 20%   10%   13%      10%       27%                      R   "     P-57  1,000 19%    9%   11%       7%       24%                      S   "     P-64  1,000 21%   10%   13%       7%       23%                      T   "     P-117 1,000 22%   15%   16%      14%       28%                      U   "     P-129 1,000 20%   11%   13%      10%       26%                      V   C-14  P-3     500  3%    4%    2%       4%       67%                      W   C-50  P-3   1,000 17%   10%   11%       7%       36%                      X   "     P-57  1,000 13%    7%    8%       5%       29%                      Y   "     P-64  1,000 15%    7%   10%       5%       31%                      Z   "     P-129 1,000 16%    9%   10%       7%       35%                      __________________________________________________________________________                                                         Flouorescent Lamp                  Polymer                                    (30,000 Lux)                             Amount                               Discoloration                      Compound                                                                            used  Discoloration in Dark          under light              Sample                                                                            Coupler                                                                             (Formula)                                                                           mg/m.sup.2                                                                          5 Days                                                                              9 Months                                                                            12 Days  3 Months  5 Months                 __________________________________________________________________________    Comparison                                                                    1   C-1   --    --    57%   52%   37%      35%       51%                      2   C-2   --    --    29%   26%   14%      13%       60%                      3   C-3   --    --    27%   25%   13%      13%       59%                      4   C-11  --    --    42%   29%   25%      22%       50%                      5   C-14  --    --     5%    7%    4%       6%       95%                      6   C-50  --    --    35%   33%   18%      17%       56%                      __________________________________________________________________________

It is apparent from the results shown in Table 2 that heat fastness,humidity fastness and light fastness are improved according to thepresent invention.

Furthermore, the polymer which may be effective to improve theadvantages of the present invention is a homopolymer or copolymer whichis composed of a monomer such that a homopolymer of said monomerexhibits higher grass transition temperature (Tg). The advantages of thepresent invention becomes more remarkable when a silver halidephotographic material is treated at a lower temperature which ispractically important conditions.

The color fastness of dye images in heat and light is remarkablyimproved and, particularly, the overall fastness is improved by adoptinga combination of a polymer having high Tg and a compound of formula(Cp-I) wherein R³² is an alkyl group having 2 carbon atoms.

EXAMPLE (2)

Samples (A-1) to (A-27) were prepared in the same manner as describedfor Sample A in Table 1 (refer to) except for using a silverchlorobromide emulsion (silver bromide: 70 mol%) in place of the silverchlorobromide emulsion (silver chloride: 98 mol%) in Sample A andchanging the coupler, the coupler solvent, the polymer and the amount ofpolymer as shown in Table 3 below.

These samples were subjected to continuous gradation exposure through anoptical wedge for sensitometry and then developed by Process (A) orProcess (B). The difference between Process (A) and Process (B) was onlyin the color development step wherein Color Developing Solution (A) wasused in Process (A) and Color Developing Solution (B), which had thesame composition as that of Color Developing Solution (A) except foreliminating benzyl alcohol, was used in Process (B), and the otherprocessing steps were the same in both Process (A) and Process (B).

Color development processing was conducted using the followingprocessing steps:

    ______________________________________                                        Color development                                                             Processing Steps                                                              ______________________________________                                        1.    Color Development                                                                            33° C.                                                                           3 min 30 sec                                   2.    Bleach-Fixing  33° C.                                                                           1 min 30 sec                                   3.    Washing with Water                                                                           28 to 35° C.                                                                     3 min 30 sec                                   ______________________________________                                    

The composition of each processing solution used for the above colordevelopment processing steps was as follows:

    ______________________________________                                        Color Developing Solution (A):                                                Diethylenetriaminepentaacetic Acid                                                                    1.0    g                                              Benzyl Alcohol          15     ml                                             Diethylene Glycol       10     ml                                             Na.sub.2 SO.sub.3       2.0    g                                              KBr                     0.5    g                                              Hydroxylamine Sulfate   3.0    g                                              4-Amino-3-methyl-N-ethyl-N-[β-                                                                   5.0    g                                              (methanesulfonamido)ethyl]-p-                                                 phenylenediamine Sulfate                                                      Na.sub.2 CO.sub.3 (monohydrate)                                                                       30     g                                              Fluorescent Whitening Agent                                                                           1.0    g                                              (4,4'-diaminostilbene type)                                                   Water to make           1      liter                                          pH                      10.1                                                  Color Developing Solution (B):                                                Diethylenetriaminepentaacetic Acid                                                                    1.0    g                                              Diethylene Glycol       10     ml                                             Na.sub.2 SO.sub.3       2.0    g                                              KBr                     0.5    g                                              Hydroxylamine Sulfate   3.0    g                                              4-Amino-3-methyl-N-ethyl-N-[β-                                                                   5.0    g                                              (methanesulfonamido)ethyl]-p-                                                 phenylenediamine Sulfate                                                      Na.sub.2 CO.sub.3 (monohydrate)                                                                       30     g                                              Fluorescent Whitening Agent                                                                           1.0    g                                              (4,4'-diaminostilbene type)                                                   Water to make           1      liter                                          Bleach-Fixing Solution:                                                       Ammonium Thiosulfate    150    ml                                             (70% by weight aqueous solution)                                              Na.sub.2 SO.sub.3       15     g                                              NH.sub.4 [Fe(III) (EDTA)]                                                                             55     g                                              EDTA · 2Na     4      g                                              Water to make           1      liter                                          pH                      6.9                                                   ______________________________________                                    

The maximum densities obtained from Process (A) and Process (B) areshown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                     Amount of                                                                     Coupler       Amount of                                                                           Reflective Density                                   Coupler                                                                            Solvent       Polymer                                                                             Color Developing                                                                       Color Developing                Sample                                                                            Coupler Solvent                                                                            (mg/m.sup.2)                                                                          Polymer                                                                             (mg/m.sup.2)                                                                        Solution (A)                                                                           Solution (B)                                                                           Remarks                __________________________________________________________________________    A-1 C-1     --   --      --    --    2.88     1.53     Comparison             A-2 C-1     --   --      P-3    500  2.91     1.35     "                      A-3 C-1     --   --      --    1000  3.06     1.17     "                      A-4 C-1     --   --      P-3   1500  2.97     0.95     "                      A-5 C-1     S-16 300     --    --    2.86     1.95     "                      A-6 C-1     "    300     P-3    500  3.04     2.02     Present                                                                       invention              A-7 C-1     "    300     P-3   1000  3.10     2.01     Present                                                                       invention              A-8 C-1     "    500     P-3   1500  2.98     2.03     Present                                                                       invention              A-9 C-3     --   --      --    --    2.63     1.20     Comparison             A-10                                                                              C-3     --   --      P-8   1000  2.61     0.90     "                      A-11                                                                              C-3     S-5  400     P-8   1000  2.72     1.63     Present                                                                       invention              A-12                                                                              C-3     S-25 400     P-8   1000  2.70     1.59     Present                                                                       invention              A-13                                                                              C-3     S-61 300     P-8   1000  2.70     1.55     Present                                                                       invention                          S-25 300                                                          A-14                                                                              C-3                  P-8   1000  2.82     2.49     Present                            S-56 200                                   invention              A-15                                                                              C-11    --   --      --    --    2.98     2.30     Comparison             A-16                                                                              C-11    --   --      P-62  1000  2.96     2.40     "                      A-17                                                                              C-11    S-9  300     P-62  1000  3.02     2.51     Present                                                                       invention              A-18                                                                              C-2     --   --      --    --    2.65     1.32     Comparison             A-19                                                                              C-2     --   --      P-57  1200  2.61     0.84     "                      A-20                                                                              C-2     S-16 150     P-57  1200  2.71     1.63     Present                                                                       invention              A-21                                                                              C-2     S-16 300     P-57  1200  2.79     1.71     Present                                                                       invention              A-22                                                                              C-2     S-56 150     P-57  1200  2.76     1.68     Present                                                                       invention                          S-16 300                                                          A-23                                                                              C-2                  P-57  1200  2.84     2.41     Present                            S-56 150                                   invention              A-24                                                                              C-25    --   --      --    --    2.59     1.24     Comparison             A-25                                                                              C-25    --   --      P-60  1000  2.48     0.68     "                      A-26                                                                              C-25    S-16 300     P-60  1000  2.57     1.67     Present                                                                       invention              A-27                                                                              C-25    S-31 300     P-60  1000  2.54     1.63     Present                                                                       invention              __________________________________________________________________________

It is apparent from the results shown in Table 3 that the samplesaccording to the present invention containing the coupler solvent havinga high boiling point and the polymer in accordance with the presentinvention are excellent in color forming ability and exhibit high colordensity even when developed with the color developing solution whichdoes not contain benzyl alcohol in comparison with the samples forcomparison.

EXAMPLE (3)

With Samples (A-1), (A-3), (A-5), (A-7), (A-9), (A-10), (A-12), (A-15),(A-16), (A-17), (A-18), (A-19), (A-21) and (A-23) processed with ColorDeveloping Solution (A) in Example 2, light fastness, heat fastness andfastness to combined high humidity and heat were evaluated according tothe test methods as shown in Example 1. The rate of decrease in imagedensity in the area having an initial density of 1.5 was determined toinvestigate the degree of fading. The results thus obtained are shown inTable 4.

                                      TABLE 4                                     __________________________________________________________________________                            Amount                                                              Coupler   of   Dark Fading   Light Fading                                Coupler                                                                            Solvent   Polymer                                                                            100° C.                                                                     80° C., 70% RH                                                                  Xenon (85,000                      Sample                                                                            Coupler                                                                            Solvent                                                                            (mg/m.sup.2)                                                                       Polymer                                                                            (mg/m.sup.2)                                                                       5 Days                                                                             12 Days  Lux) 6 Days                                                                           Remark                     __________________________________________________________________________    A-1 C-1  --   --   --   --   52%  43%      49%     Comparison                 A-3 C-1  --   --   P-3  1000 27%  23%      40%     "                          A-5 C-1  S-16 300  --   --   56%  47%      24%     "                          A-7 C-1  S-16 300  P-3  1000 26%  20%      12%     Present                                                                       invention                  A-9 C-3  --   --   --   --   32%  18%      62%     Comparison                 A-10                                                                              C-3  --   --   P-8  1000 19%  14%      50%     "                          A-12                                                                              C-3  S-25 400  P-8  1000 17%  12%      23%     Present                                                                       invention                  A-15                                                                               C-11                                                                              --   --   --   --   49%  40%      56%     Comparison                 A-16                                                                               C-11                                                                              --   --   P-62 1000 32%  27%      43%     "                          A-17                                                                               C-11                                                                              S-9  300  P-62 1000 21%  16%      12%     Present                                                                       invention                  A-18                                                                              C-2  --   --   --   --   32%  19%      63%     Comparison                 A-19                                                                              C-2  --   --   P-57 1200 16%  10%      50%     "                          A-21                                                                              C-2  S-16 300  P-57 1200 12%   7%      15%     Present                                                                       invention                           S-16 300                                                             A-23                                                                              C-2            P-57 1200 10%   6%      13%     Present                             S-56 150                                  invention                  __________________________________________________________________________

As is apparent from the results shown in Table 4, heat fastness,humidity fastness and light fastness are improved for photographicmaterials prepared according to the present invention. When employingthe polymer according to the present invention without using the couplersolvent having a high boiling point, light fastness is extremely poor,while heat fastness and humidity fastness are improved to some extent.On the contrary, heat fastness, humidity fastness and light fastness aregreatly improved by employing the coupler solvent having a high boilingpoint together with the polymer according to the present invention ascan be seen from the results shown in Table 4 above.

EXAMPLE (4)

9.2 g of Coupler (C-1) according to the present invention was dissolvedin 55 ml of ethyl acetate by heating to 60° C. The resulting couplersolution was added to a mixture of 100 g of a 16% aqueous solution ofgelatin and 10 ml of a 5% aqueous solution of sodiumdodecylbenzenesulfonate at 50° C. with stirring, and the mixture wasemulsified using a high speed stirrer (Homogenizer manufactured byNippon Seiki Seisakusho). To the resulting emulsion was then added waterso as to make 400 g whereby Emulsion (A) was prepared. The averageparticle size of Emulsion (A) was 0.14 μm.

In a manner similar to that as described above, Emulsions (B) to (K)were prepared. The particle size of the emulsion was controlled bychanging the revolution rate of the stirring blade of the homogenizer.The average particle size was measured by Nanosizer manufactured by theCoal Tar Lte. in England.

Emulsions (A) to (K) were melted by heating to 40° C. with stirring. Thestability of the emulsions with the lapse of time was evaluated. Theresults obtained are shown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________              Amount    Amount     Amount                                                                             Average Particle Size                               of        of Coupler of   Just After                                                                          After                                                                             After                                                                              After                                Coupler                                                                            Coupler                                                                            Solvent    Polymer                                                                            Preparation                                                                         24 hs.                                                                            48 hs.                                                                             72 hs.                     Emulsion                                                                           Coupler                                                                            (g)  Solvent                                                                            (g)   Polymer                                                                            (g)  (μ)                                                                              (μ)                                                                            (μ)                                                                             (μ)                                                                            Remark                 __________________________________________________________________________    A    C-1  9.2  --   --    --   --   0.14  0.25                                                                              0.56 1.10                                                                              Comparison             B    C-1  9.2  --   --    P-3  18   0.13  0.18                                                                              0.42 0.90                                                                              Comparison             C    C-1  9.2  --   --    P-63 15   0.16  0.19                                                                              0.70 1.08                                                                              "                      D    C-1  9.2  S-16 3     P-3  18   0.17  0.18                                                                              0.17 0.18                                                                              Present                                                                       invention              E    C-1  9.2  S-16 6     P-3  18   0.16  0.18                                                                              0.18 0.18                                                                              Present                                                                       invention              F    C-1  9.2  S-31 4     P-63 15   0.14  0.14                                                                              0.14 0.16                                                                              Present                                                                       invention              G    C-2  9.4  --   --    --   --   0.17  0.19                                                                              0.36 0.49                                                                              Comparison             H    C-2  9.4  --   --    P-52 12   0.19  0.22                                                                              0.45 0.93                                                                              "                      I    C-2  9.4  --   --    P-57 12   0.15  0.21                                                                              0.61 0.87                                                                              "                      J    C-2  9.4  S-16 8     P-52 12   0.14  0.14                                                                              0.15 0.17                                                                              Present                                                                       invention              K    C-2  9.4  S-25 6     P-57 12   0.18  0.18                                                                              0.20 0.21                                                                              Present                                                                       invention              __________________________________________________________________________

It is apparent from the results shown in Table 5 that the oleophilicfine particles composed of the coupler, the coupler solvent having ahigh boiling point and the polymer according to the present inventionexhibit substantially no change in particle size even after 72 hours. Onthe contrary, it can be recognized that the particle size of theemulsion for comparison increases over time. These results clearlyindicate that the emulsions according to the present invention haveexcellent stability.

EXAMPLE (5)

On a paper support, both surfaces of which were laminated withpolyethylene, were coated layers as shown in Table 6 below in order toprepare a multilayer color photographic light-sensitive material forprinting paper, which was designated Light-Sensitive Material (a). Thecoating solutions used were prepared in the following manner.

The Coating Solution for the First Layer:

19.1 g of Yellow Coupler (a) and 4.4 g of Color Image Stabilizer (b)were dissolved in a mixture of 27.2 ml of ethyl acetate and 10.9 ml ofSolvent (c) and the resulting solution was added to 185 ml of a 10%aqueous solution of gelatin containing 16 ml of a 10% aqueous solutionof sodium dodecylbenzenesulfonate. The mixture was emulsified anddispersed using a homogenizer to obtain an emulsified dispersion.Separately, to a silver chlorobromide emulsion (having a bromide contentof 80 mol% and containing 70 g of silver per kg of the emulsion) wasadded 7.0×10⁻⁴ mol of a blue-sensitive sensitizing dye shown below permol of the silver chlorobromide to prepare 90 g of a blue-sensitiveemulsion. The dispersion was mixed with emulsion, with the concentrationof the resulting mixture being controlled with gelatin, to form thecomposition shown in Table 6 below,.i.e., the coating solution for thefirst layer.

Coating solutions for the second layer to the seventh layer wereprepared in a similar manner as described for the coating solution forthe first layer. 2,4-Dichloro-6-oxy-s-triazine sodium salt was used as agelatin hardener in each layer.

The following spectral sensitizing dyes were employed in the emulsionlayers, respectively. ##STR22##

The following dyes were employed as irradiation preventing dyes in theemulsion layers, respectively. ##STR23##

The compounds used in the above-described layers have the structuresshown below, respectively. ##STR24##

                  TABLE 6                                                         ______________________________________                                                                Amount Used                                           ______________________________________                                        Seventh Layer: Protective Layer                                               Gelatin                   1.33 g/m.sup.2                                      Acryl-modified polyvinyl alcohol                                                                        0.17 g/m.sup.2                                      copolymer (degree of modification: 17%)                                       Sixth Layer: Ultraviolet Light Absorbing Layer                                Gelatin                   0.54 g/m.sup.2                                      Ultraviolet Light Absorbing Agent (h)                                                                   0.21 g/m.sup.2                                      Solvent (j)               0.09 ml/m.sup.2                                     Fifth Layer: Red-Sensitive Layer                                              Silver chlorobromide emulsion                                                                           0.26 g/m.sup.2                                      (silver bromide: 70 mol %)                                                                              (as silver)                                         Gelatin                   0.98 g/m.sup.2                                      Cyan Coupler (k)          0.41 g/m.sup.2 *1                                   Solvent (l)               0.20 ml/m.sup.2                                     Fourth Layer: Ultraviolet Light Absorbing Layer                               Gelatin                   1.60 g/m.sup.2                                      Ultraviolet Light Absorbing Agent (h)                                                                   0.62 g/m.sup.2                                      Color Mixing Preventing Agent (i)                                                                       0.05 g/m.sup.2                                      Solvent (j)               0.22 ml/m.sup.2                                     Third Layer: Green-Sensitive Layer                                            Silver chlorobromide emulsion                                                                           0.16 g/m.sup.2                                      (silver bromide: 75 mol %)                                                                              (as silver)                                         Gelatin                   1.80 g/m.sup.2                                      Magenta Coupler (e)       0.34 g/m.sup.2                                      Color Image Stabilizer (f)                                                                              0.20 g/m.sup.2                                      Solvent (g)               0.60 g/m.sup.2                                      Antistaining Agent (m)    0.08 g/m.sup.2                                      Second Layer: Color Mixing Preventing Layer                                   Gelatin                   0.99 g/m.sup.2                                      Color Mixing Preventing Agent (d)                                                                       0.08 g/m.sup.2                                      First Layer: Blue-Sensitive Layer                                             Silver chlorobromide emulsion                                                                           0.30 g/m.sup.2                                      (silver bromide: 80 mol %)                                                                              (as silver)                                         Gelatin                   1.86 g/m.sup.2                                      Yellow Coupler (a)        0.82 g/m.sup.2                                      Color Image Stabilizer (b)                                                                              0.19 g/m.sup.2                                      Solvent (c)               0.47 ml/m.sup.2                                     Support:                                                                      Polyethylene laminated paper (the polyethylene coating                        containing a white pigment (TiO.sub.2) and a bluish dye (ultra-               marine) on the first layer side)                                              ______________________________________                                         *1: 0.80 mmol/m.sup.2                                                    

Light-Sensitive Materials (b) to (Y) for comparison or according to thepresent invention were prepared in the same manner as described forLight-Sensitive Material (a) except that the composition of coupler oildroplets in the fifth layer (red-sensitive layer) of Light-SensitiveMaterial (a) was changed to those as shown in Table 7 below,respectively.

                                      TABLE 7                                     __________________________________________________________________________              Amount     Amount                                                   Light     of         of        Coupler   Amount                               Sensitive Coupler    Polymer                                                                            Coupler                                                                            Solvent                                                                            Other                                                                              of Other                             Material                                                                           Coupler                                                                            (mmol/m.sup.2)                                                                      Polymer                                                                            (g/m.sup.2)                                                                        Solvent                                                                            (g/m.sup.2)                                                                        Additives                                                                          Additives                                                                          Remark                          __________________________________________________________________________    a    C-2  0.80  --   --   S-16 0.20 --   --   Comparison                      b    "    "     P-21 1.0  --   --   --   --   "                               c    "    "     P-21 1.0  S-16 0.20 --   --   Present                                                                       Invention                       d    C-2  0.80  P-21 1.0  S-16 0.20 X-7  0.05 Present                                                                       Invention                       e    C-2  0.80  P-21 1.0  S-16 0.10 X-11 0.20 Present                                                                       Invention                       f    C-2  0.80  P-3  1.0  --   --   --   --   Comparison                      g    "    "     P-3  1.0  S-16 0.10 X-7  0.05 Present                                                             X-11 0.20 Invention                       h    C-2  0.80  --   --   S-25 0.20 --   --   Comparison                      i    "    "     P-57 1.0  --   --   --   --                                   j    "    "     P-57 1.0  S-25 0.20 --   --   Present                                                                       Invention                       k    C-2  0.80  P-62 1.0  S-25 0.20 X-11 0.20 Present                                                                       Invention                       l    C-3  0.80  --   --   S-16 0.15 --   --   Comparison                      m    "    "     P-3  1.0  S-16 0.15 --   --   Present                                                                       Invention                       n    C-3  0.80  P-21 1.0  S-16 0.20 --   --   Present                                                                       Invention                       o    C-3  0.80  P-57 1.0  S-16 0.20 X-7  0.05 Present                                                             X-11 0.20 Invention                       p    C-3  0.80  P-62 1.0  S-16 0.20 --   --   Present                                                                       Invention                       q    C-1  0.80  --   --   S-16 0.20 --   --   Comparison                      r    "    "     P-3  1.5  S-16 0.20 --   --   Present                                                                       Invention                       s    C-1  0.80  P-3  1.5  S-16 0.20 X-6  0.07 Present                                                             P*1  0.25 Invention                       t    C-1  0.80  P-57 1.2  S-16 0.25 --   --   Present                                                                       Invention                       u    C-1  0.80  P-62 1.2  S-16 0.25 --   --   Present                                                                       Invention                       v     C-11                                                                              0.80  --   --   S-16 0.20 --   --   Comparison                      w    "    "     P-3  1.2  --   --   --   --   "                               x    "    "     P-3  1.2  S-16 0.20 --   --   Present                                                                       Invention                       y     C-11                                                                              0.80  P-57 1.2  S-16 0.20 --   --   Present                                                                       Invention                       __________________________________________________________________________     *1P indicated a mixture of X9, X10 and X11 in a molar ratio of 1:5:3.    

These light-sensitive materials thus prepared were subjected to stepwiseexposure for sensitometry through each of blue, green and red filtersusing a sensitometer (FWH Type manufactured by Fuji Photo Film Co.,Ltd.; color temperature of light source: 3,200° K.). Exposure time as0.5 second in an exposure amount of 250 CMS.

Then the exposed light-sensitive materials were treated using Process(B) as described in Example 2. Fastness of the images obtained wasevaluated for yellow, magenta and cyan fastness using the same testmethods as shown in Examples 1 and 3. The rate of decrease in density inthe area having an initial density of 1.0 was determined to establishthe degree of fading. The results thus obtained are shown in Tables 8and 9.

                  TABLE 8                                                         ______________________________________                                        Yellow and Magenta*.sup.1                                                     Dark Fading                                                                                   80° C., 70% RH                                                                     Light Fading                                      100° C., 5 Days                                                                        12, Days    Xenon, 6 Days                                     ______________________________________                                        Yellow 2 to 4       3 to 4      12 to 14                                      Magenta                                                                              2 to 5       2 to 3      14 to 16                                      ______________________________________                                         *.sup.1 The rate of fading of yellow and magenta of all LightSensitive        Materials (a) to (y) was within the ranges shown in Table 8.             

                  TABLE 9                                                         ______________________________________                                        Cyan                                                                          Light- Dark Fading     Light Fading                                           Sensitive                                                                            100° C.                                                                        80° C., 70% RH                                                                     Xenon                                              Material                                                                             5 Days  12 Days     6 Days   Remark                                    ______________________________________                                        a      29%     16%         34%      Comparison                                b      17%     12%         56%      Comparison                                c      11%      7%         20%      Present                                                                       Invention                                 d       9%      6%         17%      Present                                                                       Invention                                 e       8%      6%         16%      Present                                                                       Invention                                 f      18%     11%         54%      Comparison                                g       9%      7%         17%      Present                                                                       Invention                                 h      31%     17%         36%      Comparison                                i      15%     10%         50%      Comparison                                j       7%      6%         17%      Present                                                                       Invention                                 k       6%      6%         17%      Present                                                                       Invention                                 l      31%     17%         37%      Comparison                                m      12%      9%         19%      Present                                                                       Invention                                 n      10%      6%         18%      Present                                                                       Invention                                 o       6%      6%         16%      Present                                                                       Invention                                 p       7%      7%         16%      Present                                                                       Invention                                 q      50%     47%         21%      Comparison                                r      21%     18%         12%      Present                                                                       Invention                                 s      18%     16%          8%      Present                                                                       Invention                                 t      16%     17%          8%      Present                                                                       Invention                                 u      15%     16%          8%      Present                                                                       Invention                                 v      36%     32%         27%      Comparison                                w      43%     32%         32%      Comparison                                x      17%     12%         14%      Present                                                                       Invention                                 y      11%     10%         11%      Present                                                                       Invention                                 ______________________________________                                    

It is apparent from the results shown in Tables 8 and 9 that with themultilayer color printing papers according to the present invention,light fading and dark fading are controlled with good color balance andthe fading balance of yellow, magenta and cyan is excellent in total ascompared with the comparison color printing papers. Thus, it can be seenthat the dye images obtained according to the present invention can bepreserved for a long period of time.

The same procedures as described above were conducted using YellowCouplers (Y-1), (Y-3), (Y-4) and (Y-5), and Magenta Couplers (M-1),(M-2) and (M-4) in place of (Y-2) and (M-3), respectively, and similarresults as described above were obtained. It was again observed that thelight-sensitive materials according to the present invention have anexcellent balance between yellow, magenta and cyan fading.

EXAMPLE 6

A multilayer color paper (1) was prepared by coating layers having thefollowing formulations on a paper support.

(Preparation of coating composition for 1st layer)

In 27.2 cc of ethyl acetate and 15 ml of a high-boiling solvent system(S-9/S-16-1/1 by weight) were dissolved 10.2 g of Yellow Coupler (Y-1),9.1 g of Yellow Coupler (Y-2), and 2.1 g of Dye Image Stabilizer(Cpd-2), and the resulting solution was dispersed in 185 cc of a 10%gelatin aqueous solution containing 8 cc of a 10% sodiumdodecylbenzenesulfonate aqueous solution. The dispersion was mixed withEmulsions (EM-1) and (EM-2), and a gelatin concentration was adjusted soas to have a prescribed composition to prepare a coating composition forthe 1st layer. Coating compositions for the 2nd to 7th layers wereprepared in the similar manner. Each of the layers further contained1-oxy-3,5-dichloro-s-triazine sodium salt as a gelatin hardener.Further, (Cpd-1) was used as a thickening agent. (Layer constitution)

The constitution of each layer is shown below:

In the descriptions neumerals show an amount of coatings in g/m² and anamount of silver halide emulsion shows calculated amount of silvercoated therein.

    ______________________________________                                        1st Layer (Blue-Sensitive Layer)                                              Mono-dispersed silver chloro-                                                                          0.13                                                 bromide emulsion (EM-1) spectral-                                             ly sensitized with Sensitizing                                                Dye (ExS-1)                                                                   Mono-dispersed silver chloro-                                                                          0.13                                                 bromide emulsion (EM-2) spectral-                                             ly sensitized with Sensitizing                                                Dye (ExS-1)                                                                   Gelatin                  1.86                                                 Yellow Coupler (Y-1)     0.44                                                 Yellow Coupler (Y-2)     0.39                                                 Dye Image Stabilizer (Cpd-2)                                                                           0.08                                                 Solvent (S-9)            0.35                                                 Solvent (S-16)           0.35                                                 Color Mixing Inhibitor (Cpd-18)                                                                        0.01                                                 2nd Layer (Color Mixing Preventing Layer)                                     Gelatin                  0.99                                                 Color Mixing Inhibitor (Cpd-3)                                                                         0.08                                                 3rd Layer (Green-Sensitive Layer)                                             Mono-dispersed silver chloro-                                                                          0.05                                                 bromide emulsion (EM-3)                                                       spectrally sensitized with                                                    Sensitizing Dyes (ExS-2 & 3)                                                  Mono-dispersed silver chloro-                                                                          0.11                                                 bromide emulsion (EM-4)                                                       spectrally sensitized with                                                    Sensitizing Dyes (ExS-2 & 3)                                                  Gelatin                  1.80                                                 Magenta Coupler (M-35)   0.39                                                 Dye Image Stabilizer (Cpd-4)                                                                           0.20                                                 Dye Image Stabilizer (Cpd-5)                                                                           0.02                                                 Dye Image Stabilizer (Cpd-6)                                                                           0.03                                                 Solvent (S-16)           0.12                                                 Solvent (S-7)            0.25                                                 4th Layer (Ultraviolet Absorbing Layer)                                       Gelatin                  1.60                                                 Ultraviolet Absorbent (Cpd-7/                                                                          0.70                                                 Cpd-9/Cpd-16 = 3/2/6 by weight)                                               Color Mixing Inhibitor (Cpd-11)                                                                        0.05                                                 Solvent (S-69)           0.27                                                 5th Layer (Red-Sensitive Layer)                                               Mono-dispersed silver chloro-                                                                          0.07                                                 bromide emulsion (EM-5)                                                       spectrally sensitized with                                                    Sensitizing Dyes (ExS-4 & 5)                                                  Mono-dispersed silver chloro-                                                                          0.16                                                 bromide emulsion (EM-6)                                                       spectrally sensitized with                                                    Sensitizing Dyes (ExS-4 & 5)                                                  Gelatin                  0.92                                                 Cyan Coupler (C-2)       0.32                                                 Dye Image Stabilizer (Cpd-8/                                                                           0.17                                                 Cpd-9/Cpd-10 = 3/4/2 by weight)                                               Color Mixing Inhibitor (Cpd-18)                                                                        0.02                                                 Color Mixing Inhibitor (Cpd-3)                                                                         0.02                                                 Solvent (S-9)            0.10                                                 Solvent (S-16)           0.10                                                 Solvent (S-5)            0.10                                                 6th Layer (Ultraviolet Absorbing Layer)                                       Gelatin                  0.54                                                 Ultraviolet Absorbent (Cpd-7/Cpd-8/                                                                    0.21                                                 Cpd-9 = 1/5/3 by weight)                                                      Solvent (S-69)           0.08                                                 7th Layer (Protective Layer)                                                  Gelatin                  1.33                                                 Acryl-modifed polyvinyl alcohol                                                                        0.17                                                 (degree of modification: 17%)                                                 Liquid paraffin          0.03                                                 ______________________________________                                    

In the emulsion layers, (Cpd-12) and (Cpd-13) were used asanti-irradiation dyes.

In each layer, Alkanol XC (produced by E. I. Du pont), sodiumalkylbenzenesulfonate, succinic ester, and Megafac F-120 (produced byDai-Nippon Ink K.K.) were used as dispersing agents or coating aids; and(Cpd-14), (Cpd-15), and (Cpd-17) were used as stabilizers for silverhalide.

The compounds used in the sample preparation are shown below: ##STR25##

Emulsions used in the sample preparation are tabulated below.

    ______________________________________                                                         Mean      Br                                                 Emulsion                                                                             Shape of  Grain Size*                                                                             Content                                                                              Coefficient                                 No.    Grains    (μm)   (mol %)                                                                              of Variation**                              ______________________________________                                        EM-1   cubic     1.0       80     0.08                                        EM-2   cubic      0.75     80     0.07                                        EM-3   cubic     0.5       83     0.09                                        EM-4   cubic     0.4       83     0.10                                        EM-5   cubic     0.5       73     0.09                                        EM-6   cubic     0.4       73     0.10                                        ______________________________________                                         Note:                                                                         *A mean of an edge length based on a projected area.                          **A ratio of a standard deviation(s) to a mean grain size (-d), which         represents (s/-d).                                                       

Samples (2) to 13) were produced in the same manner as for Sample (1)except for alteration shown in Table 10 shown.

                                      TABLE 10                                    __________________________________________________________________________    Alteration on Sample (1)                                                      Sample                                                                        No. Blue-Sensitive Layer                                                                     Green-Sensitive Layer                                                                     Red-Sensitive Layer                                __________________________________________________________________________    (1)   --         --          --                                               (2)   --         --        P-56 (0.30 g/m.sup.2) was added.                   (3)   --         --        P-56 (0.90 g/m.sup.2) was added.                   (4) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-57 (0.90 g/m.sup.2) was added.                       was added. was added.                                                     (5) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-3 (0.90 g/m.sup.2) was added.                        was added. was added.                                                     (6) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-5 (0.90 g/m.sup.2) was added.                        was added. was added.                                                     (7) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-57 (0.90 g/m.sup.2) was added,                       was added. was added.  and C-11 was replaced with                                                    C-2.                                               (8) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-57 (0.90 g/m.sup.2) was added,                       was added. was added.  and C-11 was replaced with                                                    C-1.                                               (9) P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-57 (0.90 g/m.sup.2) was added,                       was added. was added.  and all the solvents were                                                     replaced with S-69.                                (10)                                                                              P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2)                                                                     P-57 (0.90 g/m.sup.2) was added,                       was added. was added, and all the                                                                    and all the solvents were                                         solvents were replaced                                                                    replaced with S-25.                                               with S-25.                                                     (11)                                                                              P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2) was                                                                 P-57 (0.90 g/m.sup.2) was added.                       was added  added, and M-35 was                                                           replaced with M-1.                                             (12)                                                                              P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2) was                                                                 P-57 (0.90 g/m.sup.2) was added.                       was added. added, and M-35 was                                                           replaced with M-2.                                             (13)                                                                              P-57 (0.30 g/m.sup.2)                                                                    P-57 (0.30 g/m.sup.2) was                                                                 P-57 (0.90 g/m.sup.2) was added,                       was added. added, M-35 was replac-                                                                   C-11 was replaced with C-1,                                       ed with M-1, and all                                                                      and all the solvents were                                         the solvents were                                                                         replaced with S-25.                                               replaced with S-25.                                            __________________________________________________________________________

Each of Samples above was exposed to light through an optical wedge andsubjected to development processing according to the followingprocedure.

    ______________________________________                                        Processing Step                                                                             Temperature      Time                                           ______________________________________                                        Color Development                                                                           38° C.    1'40"                                          Blix          30-34° C. 1'00"                                          Rinsing (1)   30-34° C. 20"                                            Rinsing (2)   30-34° C. 20"                                            Rinsing (3)   30-34° C. 20"                                            Drying        70-80° C. 50"                                            ______________________________________                                    

Rinsing was carried out in a counter-current system using three tanksfrom (3) toward (1).

The processing solutions used in the development had the followingformulations.

    ______________________________________                                        Color Developer Formulation:                                                  Water                     800    ml                                           Diethylenetriaminepentaacetic acid                                                                      1.0    g                                            1-Hydroxyethylidene-1,1-diphosphonic                                                                    2.0    g                                            acid                                                                          Nitrilotriacetic acid     2.0    g                                            Benzyl alcohol            16     ml                                           Diethylene glycol         10     ml                                           Sodium sulfite            2.0    g                                            Potassium bromide         0.5    g                                            Potassium carbonate       30     g                                            N-Ethyl-N-(-methanesulfonamido-                                                                         5.5    g                                            ethyl)-3-methyl-4-aminoaniline                                                sulfate                                                                       Hydroxylamine sulfate     3.0    g                                            Fluorescent brighteing agent                                                                            1.5    g                                            ("WHITEX 4 B" produced by Sumitomo                                            Chemical Co., Ltd.)                                                           Water to make             1000   ml                                           pH = 10.25                (25° C.)                                     Blix Bath Formulation:                                                        Water                     400    ml                                           Ammonium thiosulfate (70%)                                                                              200    ml                                           Sodium sulfite            20     g                                            Ammonium (ethylenediaminetetra-                                                                         60     g                                            acetato) iron (III)                                                           Disodium ethylenediaminetetraacetate                                                                    10     g                                            Water to make             1000   ml                                           pH = 7.00                 (25° C.)                                     Rinsing Solution:                                                             Benzotriazole             1.0    g                                            Ethylenediamine-N,N,N',N'-tetra-                                                                        0.3    g                                            methylenephosphonic acid                                                      Water to make             1000   ml                                           pH = 7.50                 (25° C.)                                     ______________________________________                                    

In order to evaluate the thus processed samples for image fastness toheat, wet heat, and light, the samples were allowed to stand in a darkplace under a dry heat condition (80° C.) for 1 month or under a wetheat condition (80° C., 70% RH) for 2 weeks or exposed to light in axenontest apparatus (ca. 100,000 lux) for 8 days. The degree ofdiscoloration was determined by obtaining a reduction percentage in cyan(G), magenta (R) or yellow (B) color density from the initial density of1.5 in the case of the heat and wet heat tests or the initial density of1.0 in the case of the light test. The results obtained are shown inTables 11-13.

                  TABLE 11                                                        ______________________________________                                                Decoloration under dark and high                                      Sample  temperature 80° C., for 1 Month                                No.     B             G        R                                              ______________________________________                                         (1)    4             2        43                                              (2)    4             2        28                                              (3)    4             2        11                                              (4)    4             0        10                                              (5)    4             0        17                                              (6)    4             0        34                                              (7)    4             0         7                                              (8)    4             0        20                                              (9)    4             0        19                                             (10)    4             0        18                                             (11)    4             10       11                                             (12)    4             12       11                                             (13)    3             10       35                                             ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                                Decoloration under humidity and hot                                   Sample  temperature 80° C., 70% RH, for 2 Wks.                         No.     B            G         R                                              ______________________________________                                         (1)    4            2         18                                              (2)    4            2         9                                               (3)    4            2         4                                               (4)    3            0         3                                               (5)    3            0         6                                               (6)    3            0         14                                              (7)    3            0         2                                               (8)    3            0         25                                              (9)    3            0         3                                              (10)    3            2         7                                              (11)    3            12        3                                              (12)    3            6         3                                              (13)    3            14        30                                             ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                                 Decoloration with light                                              Sample   Xenon, for 8 Days                                                    No.      B             G       R                                              ______________________________________                                         (1)     26            22      30                                              (2)     26            22      25                                              (3)     26            22      19                                              (4)     18            17      18                                              (5)     18            17      24                                              (6)     18            17      26                                              (7)     18            17      21                                              (8)     18            17      19                                              (9)     18            17      17                                             (10)     18            35      22                                             (11)     18            64      18                                             (12)     18            35      18                                             (13)     18            66      21                                             ______________________________________                                    

The following considerations can be derived from the results of Tables11-13.

(1) The discoloration inhibitory effect of the polymer according to thepresent invention can be enhanced as the amount of the polymer addedincreases, as can be seen from the results of Samples (1), (2), and (3).

(2) The higher the glass transition point of the polymer, the higher thediscoloration inhibitory effect, as can be seen from the results ofSamples (4), (5), and (6).

(3) Compounds of formula (Cp-I) wherein R³² is an ethyl group aresuperior than those wherein R³² is a methyl group in terms of inclusivedye image fastness and color balance of discoloration when used incombination with the polymers, as can be seen by comparing Samples (5),(7), and (8).

(4) Phthalic esters as high-boiling solvents for couplers are inferiorin performances to phosphoric esters and fatty acid esters, as can beseen by comparing Samples (5), (9), and (10) and comparing Samples (8)and (13).

(5) Four-equivalent pyrazolone couplers undergo serious discoloration ascompared with yellow and cyan couplers even when used in combinationwith the polymer of the present invention, thus resulting in poor colorbalance, as can be seen from the results of Samples (11) and (13).

(6) With the glass transition points (Tg) being close to each other,polymers comprising an acrylamide monomer tend to produce greatereffects than those comprising an acrylate monomer, as can be seen bycomparing Samples (3) and (5).

EXAMPLE 7

Multilayer color papers were produced in the same manner as for Samples(1) to (13) of Example 6, except that the silver halide emulsions usedin Example 6 (EM-1 to EM-6) were replaced with EM-7 to EM-12 astabulated below, respectively. The resulting color papers weredesignated as Samples (14) to (26).

Each of Samples was processed according to the proceeding steps statedbelow.

    ______________________________________                                                         Mean      Br                                                 Emulsion                                                                             Shape of  Grain Size*                                                                             Content Coefficient                                No.    Grains    (μm)   (mol %) of Variation**                             ______________________________________                                        EM-7   cubic     1.1       1.0     0.10                                       EM-8   cubic     0.8       1.0     0.10                                       EM-9   cubic     0.45      1.5     0.09                                       EM-10  cubic     0.34      1.5     0.09                                       EM-11  cubic     0.45      1.5     0.09                                       EM-12  cubic     0.34      1.6     0.10                                       ______________________________________                                        Processing Step  Temperature                                                                              Time                                              ______________________________________                                        Color Development                                                                              35° C.                                                                            45"                                               Blix             30-35° C.                                                                         45"                                               Rinsing (1)      30-35° C.                                                                         20"                                               Rinsing (2)      30-35° C.                                                                         20"                                               Rinsing (3)      30-35° C.                                                                         20"                                               Rinsing (4)      30-35° C.                                                                         30"                                               Drying           70-80° C.                                                                         60"                                               ______________________________________                                         Note:                                                                         *, **The same meanings as in Example 6.                                  

The rinsing was carried out in a counter-current system using threetanks from (4) toward (1).

The processing solutions used in the development processing had thefollowing formulations.

    ______________________________________                                        Color Developer Formulation:                                                  Water                    800    ml                                            Ethylenediamine-N,N,N,N-tetra-                                                                         1.5    g                                             methylenephosphonic acid                                                      Triethylenediamine(1,4-diaza-                                                                          5.0    g                                             Sodium chloride          1.4    g                                             Potassium carbonate      25     g                                             N-Ethyl-N-(β-methanesulfonamido-                                                                  5.0 g                                                ethyl)-3-methyl-4-aminoaniline                                                sulfate                                                                       N,N-Diethylhydroxylamine 4.2    g                                             Fluorescent brightening agent                                                                          2.0    g                                             ("UVITEX CK" produced by Chiba                                                Geigy)                                                                        Water to make            1000   ml                                            pH = 10.10               (25° C.)                                      Blix Bath Formulation:                                                        Water                    400    ml                                            Ammonium thiosulfate (70%)                                                                             100    ml                                            Sodium sulfite           18     g                                             Ammonium (ethylenediaminetetra-                                                                        55     g                                             acetato)iron (III)                                                            Disodium ethylenediaminetetraacetate                                                                   3      g                                             Ammonium bromide         40     g                                             Glacial acetic acid      8      g                                             Water to make            1000   ml                                            pH = 5.5                 (25° C.)                                      Rinsing Solution Formulation:                                                 Deionized water (Ca content and                                               Mg content each is 3 ppm or less)                                             ______________________________________                                    

What is claimed is:
 1. A silver halide color photographic materialcomprising a support having thereon at least one silver halidephotographic emulsion layer containing a dispersion of oleophilic fineparticles containing at least one diffusion resistant oil-solublecoupler which forms a substantially nondiffusible dye upon coupling withan oxidation product of an aromatic primary amine developing agent andat least one water-immiscible coupler solvent having a melting point ofnot more than 100° C. and a boiling point of not less than 140° C.,wherein said oil-soluble coupler is represented by formula (Cp-I),(Cp-II), or (Cp-III), defined below, and the dispersion of oleophilicfine particles is a dispersion obtained by emulsifying or dispersing asolution containing at least one of said couplers, at least one of saidcoupler solvents, and at least one water-insoluble and an organicsolvent-soluble polymer, which is a homopolymer or copolymer composed ofat least one repeating unit in an amount of not less than 35 mol% whichdoes not have an acid group in the main chain or side chain thereof,wherein the repeating unit is a repeating unit which, when the polymeris a homopolymer having a molecular weight of at least 20,000 formedexclusively by the repeating unit, provides a polymer having a glasstransition temperature (Tg) of 50° C. or higher; ##STR26## wherein R³¹represents an alkyl group, a cycloalkyl group, an aryl group or aheterocyclic group; R³² represents an acylamino group, or an alkyl grouphaving 2 or more carbon atoms; R³³ represents a hydrogen atom, a halogenatom, an alkyl group or an alkoxy group; with proviso R³¹ represents anaryl group when R³² is an acylamino group; Z³¹ represents a hydrogenatom, or a releasable group when Z³¹ reacts with an oxidation productsof an aromatic primary amine color developing agent ##STR27## wherein Arrepresents an aryl group; R²¹ represents a hydrogen atom; an acyl group,or an aliphatic or aromatic sulfonyl group; R²² represents a halogenatom, or an alkoxy group; R²³ represents an alkyl group, an aryl group,a halogen atom, an alkoxy group, an aryloxy group, an acylamino group,an imido group, a sulfonamido group, an alkoxycarbonyl group, acarbamoyl group, a sulfamoyl group, an alkylthio group, or a sulfonylgroup; R²⁷ represents an alkyl group, an alkoxy group, or an aryloxygroup; R²⁹ represents a hydrogen atom, a halogen atom, a hydroxyl group,an alkyl group, an alkoxy group, or an aryl group; R²⁸ represents anamino group, acylamino group, an ureido group, an alkoxy carbonylaminogroup, an imido group, a sulfonamido group, a sulfamoylamino group, analkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group,or an alkylthio group; provided that at least one of R²⁷ and R²⁹represents an alkoxy group; m¹ and m² each represents an integer of 1 to4; and m³ represent 0 or an integer of 1 to 3 ##STR28## wherein R²⁴represents a hydrogen atom or a substituent group; Z²¹ represents ahydrogen atom or a releasable group when Z²¹ reacts with an oxidationproduct of an aromatic primary amine color developing agent; Z²², Z²³and Z²⁴ each represents ##STR29## --N' or --NH--, including that atleast one of bondings Z²⁴ -Z²³ and Z²³ -Z²² is double-bond and the restthereof is a single-bond, and a bonding Z²³ -Z²² is a part of anaromatic ring when Z²³ -Z²² is a carbon to carbon double-bond.
 2. Thesilver halide color photographic material as claimed in claim 1, whereinthe repeating unit which does not have an acid group has a group of##STR30## in the main chain or side chain thereof.
 3. The silver halidecolor photographic material as claimed in claim 2, wherein the repeatingunit which does not have an acid group has a group of ##STR31## in themain chain or side chain thereof.
 4. The silver halide colorphotographic material as claimed in claim 2, wherein the repeating unitwhich does not have an acid group has a group of ##STR32## in the mainchain or side chain thereof (wherein G₁ and G₂ each represents ahydrogen atom, substituted or unsubstituted alkyl group, or substitutedor unsubstituted aryl group, provided that G₁ and G₂ do notsimultaneously represent a hydrogen atom).
 5. A silver halide colorphotographic material according to claim 1, wherein at least one couplerof formula (Cp-I) as a cyan coupler, and at least one coupler offormulae (Cp-II) and (Cp-III) as magenta coupler are containedrespectively.